Orientador: Elias Taylor Durgante Severo / Banca: Claudio Angeli Sansigolo / Banca: Adriano Wagner Ballarin / Banca: Rosilei Aparecida Garcia / Banca: José Otavio Brito / Resumo: A madeira é um dos mais versáteis materiais de construção. Entretanto, considerando as pressões ambientais e a escassez de madeira nativa nas regiões Sul e Sudeste, deve-se utilizar madeiras alternativas. O gênero eucalipto se apresenta como uma solução para esse problema, porém possui limitações, tais como, altos níveis de tensões de crescimento, baixa permeabilidade e problemas de secagem, alta retratibilidade e susceptibilidade a fungos deterioradores. Uma forma comercialmente atrativa de se melhorar a estabilidade dimensional e a durabilidade biológica deste produto é a termorretificação da madeira logo após a sua secagem. Esse trabalho teve como objetivo avaliar o efeito da termorretificação sob diferentes condições de temperatura na qualidade da madeira de Eucalyptus grandis Hill ex Maiden. Para tanto, foram usadas tábuas provenientes de toras de Eucalyptus grandis, com cerca de 5,9 anos de idade, da empresa Duratex-SA. Cada uma das tábuas foi seccionada de modo a fornecer peças controle e outras destinadas para a termorretificação, com temperaturas finais de 140ºC, 160ºC, 180ºC, 200ºC e 220ºC. A qualidade da madeira foi determinada pelos seguintes ensaios: (1) perda de massa e variação da espessura das tábuas; (2) propriedades físicas (massa específica básica, a 0%, a 12,0% e a 17,5% de umidade, teor de umidade de equilíbrio, inchamentos volumétricos e lineares, coeficientes de retratibilidade e fator anisotrópico); (3) resistência a fungos deterioradores; e (4) propriedades mecânicas (compressão paralela às fibras, flexão estática e dureza Janka normal às fibras). Os resultados mostraram que: (1) a perda de massa das tábuas de E. grandis aumenta exponencialmente entre 0,004% e 5,7% com o aumento da temperatura de termorretificação de 140ºC até 220ºC; (2) na região próxima à medula há uma variação... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The wood is one of the most versatile building materials, however considering the environmental pressures associated with lack of native wood in the South and Southeast region, alternatives woods must be used. The Eucalyptus species are a solution to this problem however they have limitations such high levels of growth stress, high shrinkage, low permeability, drying defects and susceptibility to rot fungi. A commercially attractive way to improve the dimensional stability and durability of these products is this retification® process after its drying. The objetive of this work was evaluating the effect of retification®, under different temperatures on the quality of the Eucalyptus grandis Hill ex Maiden wood. In order to do it so, were used logs of Eucalyptus grandis trees, with 5.9 years of age from company Duratex-SA. Each board was cutting to provide pieces and those designed with control and retified® with temperatures of 140ºC, 160ºC, 180ºC, 200ºC and 220ºC. The quality of retified® wood was determined by the following tests (1) mass loss and tickness variation of boards; (2) physical properties (densities at 0%, 12.0% and 17.5% of moisture content, equilibrium moisture content, volumetric and linears swelling, shrinkage coeficient and anisotropic factor); (3) decay resitance of wood; and (4) mechanical properties (compression parallel to grain, static bending and Janka hardness perpendicular to grain). The results showed that: (1) the mass loss of Eucalyptus grandis boards exponentially increases from 0.004% to 5.7% with an increase of retification® temperature; (2) near pith there is a variation in the boards thickness reduction of up 99.6% with an increase of treatment temperature, while near bark this variation was of up to 18.5%; (3) with increase retification® temperature has an significant improvements on moisture content and volumetric, tangential, radial... (Complete abstract click electronic access below) / Doutor

Made available in DSpace on 2014-06-11T19:30:20Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-08-31Bitstream added on 2014-06-13T20:40:16Z : No. of bitstreams: 1 vitericabezas_wp_me_botfca.pdf: 276987 bytes, checksum: fefb989fa21883ab05774fb93da9941f (MD5) / A produção de mudas da espécie Eucalyptus grandis x Eucalyptus urophylla tem crescido muito nos últimos anos no Brasil, devido a sua boa adaptação nos diferentes solos e regiões, possuindo comportamentos diferentes quanto à exigência nutricional em diferentes tipos de substrato que o mercado oferece. O conhecimento desses comportamentos trará benefícios econômicos e diminuição dos impactos ambientais causados pelo uso excessivo de fertilizantes. Neste trabalho buscou-se avaliar o efeito de doses de fósforo em três tipos de substratos na produção de mudas de Eucalyptus grandis x Eucalyptus urophylla. O experimento foi inteiramente casualizado em fatorial 3x4, utilizando 3 substratos e 4 doses de fósforo na base, totalizando 12 tratamentos distribuídos em 4 parcelas com 25 plantas. O adubo usado na fertilização de base foi o superfosfato simples e as doses foram de 0, 160, 320 e 480 g por m3 de substrato. Os substratos utilizados foram: Carolina Soil® a base de turfa, vermiculita e casca de arroz carbonizada; substrato Mecplant® a base de casca de pinus e vermiculita e substrato a base de fibra de coco e vermiculita. As avaliações do experimento constituíram-se de análise química do substrato e características morfológicas das mudas: altura da parte aérea, diâmetro do coleto, massas secas da parte aérea e radicular e qualidade de raiz. Em função dos resultados obtidos pode-se inferir que para o substrato Carolina Soil® a dose que apresentou mudas com maior desenvolvimento foi a de 320 g m-3. Para o substrato fibra de coco + vermiculita foi a de 160 g m-3 e para o substrato a Mecplant® tanto na dose zero quanto na de 480 g m-3 apresentaram resultados semelhantes, indicando a não necessidade de aplicação de P na adubação de base neste substrato. Os três substratos produziram mudas semelhantes e dentro do padrão de qualidade adequado / The production of cuttings of the species Eucalyptus grandis x Eucalyptus urophylla has grown significantly in recent years in Brazil due to its good adaptation to different types of soil and region, having different behaviors a far as its nutritional demands on the different kinds of substrate offered by the market. Knowledge of these behaviors will bring economic benefit and a diminishing of the environmental impact caused by the excessive use of fertilizers. This investigation sought to validate the effect of doses of phosphorus on three types of substrate in the production of cuttings of Eucalyptus grandis x Eucalyptus urophylla. The experiment was entirely done on 3x4 factorial, using 3 substrates of 4 doses of phosphorous on the base, totaling 12 applications distributed among 4 parcels with 25 plants each. The fertilizer used for the base was a simple superphosphate and the doses were 0, 160, 320 and 480 g per m3 of substrate. The substrates used were: truffle based Carolina Soil®, vermiculite and carbonized rice shells, vermiculite and pinus shell based Mecplant® and coconut fiber and vermiculite substrate. Evaluations in the experiment include chemical analysis of the substrate and morphological characteristics of the cuttings: height of the airborne area, stalk diameter, dry spots on the airborne area and root and overall quality of the root. From the obtained results, it’s possible to infer that for the Carolina Soil® substrate, the dosage that showed the best growth was 320 g m3. For the coconut + vermiculite substrate the best results came with 160 g m-3 and for the Mecplant® substrate, both the zero dose and the 480 g m3 showed similar results, indicating that there isn’t a need for the application of P on the fertilizing of the base of this substrate. The three substrates will produce similar cuttings and within an adequate pattern of quality

Os cofatores de ferro-enxofre [Fe-S] estão entre os mais versáteis e antigos cofatores enzimáticos encontrados na natureza. As células têm explorado as propriedades eletrônicas e estruturais destes cofatores inorgânicos para uma ampla variedade de atividades incluindo a transferência de elétrons, a catálise e a ativação de substratos. Um grande número de proteínas está envolvido na biogênese dos cofatores [Fe-S], e este processo pode ser dividido em três etapas principais: (i) formação do enxofre elementar, (ii) montagem do cofator [Fe-S], e (iii) inserção do cofator em apoproteínas. As plantas realizam fotossíntese e respiração, dois processos que requerem proteínas Fe-S, sendo os únicos organismos em que a biossíntese destas proteínas é compartimentalizada. Diversos fatores afetam o desenvolvimento das plantas, entre eles, a temperatura baixa, fator limitante à produtividade e à distribuição geográfica das plantas, incluindo Eucalyptus grandis, uma espécie com grande importância econômica. Devido a esse fato, foi realizada uma análise transcricional dos genes codificados pelo sistema ISC de biossíntese de cofatores [Fe-S] NFS1, ISA1 e ISU1 de E. grandis por meio de PCR quantitativa (RT-qPCR), após plântulas desta espécie serem submetidas ao tratamento de frio. O gene NFS1 teve sua expressão reprimida nas primeiras 48 horas de tratamento, porém, após esse período observa-se um aumento da expressão gênica em relação à condição controle. O genes ISU1 e ISA1 apresentaram maior expressão gênica nas primeiras duas horas de tratamento, diminuindo drasticamente logo após este período. Foi verificado um aumento na quantidade relativa de Fe e S nos nas plântulas submetidas ao tratamento de frio, indicando um possível aumento na quantidade de cofatores [Fe-S] requeridos para o reestabelecimento da homeostase celular. As bactérias, por sua vez, desenvolveram pelo menos três sistemas de biossíntese, altamente conservados, que estão envolvidos na formação dos cofatores [Fe-S], sendo estes NIF, ISC e SUF. Em muitas proteobactérias, a regulação da produção de cofatores [Fe-S] pelos sistemas ISC e SUF é controlada por uma única proteína, IscR, pertencente à família de reguladores Rrf2. A proteína IscR possui um domínio de ligação ao DNA na região N-terminal e um segundo domínio de ligação de cofatores com três resíduos de cisteínas (Cys) altamente conservados. A ligação de um cofator do tipo [2Fe-2S] reprime a transcrição do seu próprio promotor in vitro. O genoma de Azotobacter vinelandii não inclui um sistema SUF completo e, portanto, permite o estudo dos efeitos da regulação de IscR não relacionada a SUF. No presente trabalho, objetivamos analisar a expressão do operon isc em linhagens selvagens e mutantes para IscR de A. vinelandii por meio das técnicas de sequenciamento do transcritoma e RT-qPCR. As substituições das Cys92, Cys104, His107 e a deleção de 120 pb da região codificadora do segundo domínio de IscR levaram à indução de um aumento da expressão de todo o operon isc. Notou-se também uma diferença fenotípica clara no tamanho das colônias portadoras das substituições de Cys e His, sendo estas menores em relação à linhagem selvagem. As substituições das Cys98 e Cys111, ou ainda a dupla substituição Cys98/111 não levaram a alteração da expressão do operon. A ligação ou não do cofator [Fe-S] é, portanto, responsável pela regulação do operon isc em A. vinelandii, bem como, de outros operons codificadores de proteínas envolvidas em cadeias tranportadoras de elétrons. / The iron-sulfur clusters [Fe-S] are among the oldest and most versatile enzyme cofactors found in nature. The cells have explored the structural and electronic properties of these inorganic clusters for a wide variety of activities including electron transfer, catalysis and activation of substrates. A large number of proteins is involved in the biogenesis of the [Fe-S] clusters, and this process can be divided into three main steps: (i) formation of elemental sulfur, (ii) assembly of the [Fe-S] cluster and (iii) insertion into apoproteins. Plants perform photosynthesis and respiration, two processes that require Fe-S protein, and in these organisms the synthesis of these proteins is compartmentalized. Several factors affect the development of plants, among them, the low temperature is a limiting factor to productivity and geographical distribution of plants, including Eucalyptus grandis, a specie with great economic importance. Due to this fact, we performed a transcriptional analysis by quantitative PCR (RT-qPCR) of the genes encoded by the E. grandis [Fe-S] cluster ISC system NFS1, ISA1 and ISU1 after seedlings were submitted to the chilling treatment. The NFS1 gene expression is repressed in the first 48 hours of treatment, but after this period there was an increase in gene expression relating to the control condition. The genes ISU1 and ISA1 showed higher gene expression in the first two hours of treatment, followed by a sharp decrease. There was an increase in the relative amount of Fe and S in the seedlings subjected to cold treatment, indicating a possible increase in the amount of [Fe-S] clusters, required for the reestablishment of cellular homeostasis. Bacteria have developed at least three synthesis systems, highly conserved, which are involved in the formation of Fe-S proteins, NIF, ISC and SUF. In many proteobacteria, the regulation of clusters production by ISC and SUF is controlled by a single protein, IscR, belonging to the Rrf2 regulators family. The protein IscR has a DNA binding site at the N-terminal domain and second cofactors binding domain with three cysteine residues (Cys) highly conserved. The binding of a [2Fe-2S] cluster represses the transcription of its own promoter in vitro. The genome of Azotobacter vinelandii does not include a full SUF system and thus permits the study of the effects of IscR regulation unrelated to SUF. In this study, the aim was to analyze the expression of isc operon in wild type and mutant strains of A. vinelandii IscR by the techniques of the transcriptome sequencing and qRT-PCR. The replacement of Cys92, Cys104, His107 and a deletion of 120 bp region encoding the second IscR domain led to an increased expression of the whole isc operon. It also showed a clear phenotypic difference in colonies size in the strains carrying the substitutions of His and Cys, it was smaller compared to the wild type strain. The replacement of Cys98 and Cys111, or the double substitution Cys98/111 not led to an altered operon expression. The [Fe-S] cluster binding or not, is therefore responsible for the regulation of the isc operon in A. vinelandii as well as of other operons encoding proteins involved in electron tranport chains.

Os cofatores de ferro-enxofre [Fe-S] estão entre os mais versáteis e antigos cofatores enzimáticos encontrados na natureza. As células têm explorado as propriedades eletrônicas e estruturais destes cofatores inorgânicos para uma ampla variedade de atividades incluindo a transferência de elétrons, a catálise e a ativação de substratos. Um grande número de proteínas está envolvido na biogênese dos cofatores [Fe-S], e este processo pode ser dividido em três etapas principais: (i) formação do enxofre elementar, (ii) montagem do cofator [Fe-S], e (iii) inserção do cofator em apoproteínas. As plantas realizam fotossíntese e respiração, dois processos que requerem proteínas Fe-S, sendo os únicos organismos em que a biossíntese destas proteínas é compartimentalizada. Diversos fatores afetam o desenvolvimento das plantas, entre eles, a temperatura baixa, fator limitante à produtividade e à distribuição geográfica das plantas, incluindo Eucalyptus grandis, uma espécie com grande importância econômica. Devido a esse fato, foi realizada uma análise transcricional dos genes codificados pelo sistema ISC de biossíntese de cofatores [Fe-S] NFS1, ISA1 e ISU1 de E. grandis por meio de PCR quantitativa (RT-qPCR), após plântulas desta espécie serem submetidas ao tratamento de frio. O gene NFS1 teve sua expressão reprimida nas primeiras 48 horas de tratamento, porém, após esse período observa-se um aumento da expressão gênica em relação à condição controle. O genes ISU1 e ISA1 apresentaram maior expressão gênica nas primeiras duas horas de tratamento, diminuindo drasticamente logo após este período. Foi verificado um aumento na quantidade relativa de Fe e S nos nas plântulas submetidas ao tratamento de frio, indicando um possível aumento na quantidade de cofatores [Fe-S] requeridos para o reestabelecimento da homeostase celular. As bactérias, por sua vez, desenvolveram pelo menos três sistemas de biossíntese, altamente conservados, que estão envolvidos na formação dos cofatores [Fe-S], sendo estes NIF, ISC e SUF. Em muitas proteobactérias, a regulação da produção de cofatores [Fe-S] pelos sistemas ISC e SUF é controlada por uma única proteína, IscR, pertencente à família de reguladores Rrf2. A proteína IscR possui um domínio de ligação ao DNA na região N-terminal e um segundo domínio de ligação de cofatores com três resíduos de cisteínas (Cys) altamente conservados. A ligação de um cofator do tipo [2Fe-2S] reprime a transcrição do seu próprio promotor in vitro. O genoma de Azotobacter vinelandii não inclui um sistema SUF completo e, portanto, permite o estudo dos efeitos da regulação de IscR não relacionada a SUF. No presente trabalho, objetivamos analisar a expressão do operon isc em linhagens selvagens e mutantes para IscR de A. vinelandii por meio das técnicas de sequenciamento do transcritoma e RT-qPCR. As substituições das Cys92, Cys104, His107 e a deleção de 120 pb da região codificadora do segundo domínio de IscR levaram à indução de um aumento da expressão de todo o operon isc. Notou-se também uma diferença fenotípica clara no tamanho das colônias portadoras das substituições de Cys e His, sendo estas menores em relação à linhagem selvagem. As substituições das Cys98 e Cys111, ou ainda a dupla substituição Cys98/111 não levaram a alteração da expressão do operon. A ligação ou não do cofator [Fe-S] é, portanto, responsável pela regulação do operon isc em A. vinelandii, bem como, de outros operons codificadores de proteínas envolvidas em cadeias tranportadoras de elétrons. / The iron-sulfur clusters [Fe-S] are among the oldest and most versatile enzyme cofactors found in nature. The cells have explored the structural and electronic properties of these inorganic clusters for a wide variety of activities including electron transfer, catalysis and activation of substrates. A large number of proteins is involved in the biogenesis of the [Fe-S] clusters, and this process can be divided into three main steps: (i) formation of elemental sulfur, (ii) assembly of the [Fe-S] cluster and (iii) insertion into apoproteins. Plants perform photosynthesis and respiration, two processes that require Fe-S protein, and in these organisms the synthesis of these proteins is compartmentalized. Several factors affect the development of plants, among them, the low temperature is a limiting factor to productivity and geographical distribution of plants, including Eucalyptus grandis, a specie with great economic importance. Due to this fact, we performed a transcriptional analysis by quantitative PCR (RT-qPCR) of the genes encoded by the E. grandis [Fe-S] cluster ISC system NFS1, ISA1 and ISU1 after seedlings were submitted to the chilling treatment. The NFS1 gene expression is repressed in the first 48 hours of treatment, but after this period there was an increase in gene expression relating to the control condition. The genes ISU1 and ISA1 showed higher gene expression in the first two hours of treatment, followed by a sharp decrease. There was an increase in the relative amount of Fe and S in the seedlings subjected to cold treatment, indicating a possible increase in the amount of [Fe-S] clusters, required for the reestablishment of cellular homeostasis. Bacteria have developed at least three synthesis systems, highly conserved, which are involved in the formation of Fe-S proteins, NIF, ISC and SUF. In many proteobacteria, the regulation of clusters production by ISC and SUF is controlled by a single protein, IscR, belonging to the Rrf2 regulators family. The protein IscR has a DNA binding site at the N-terminal domain and second cofactors binding domain with three cysteine residues (Cys) highly conserved. The binding of a [2Fe-2S] cluster represses the transcription of its own promoter in vitro. The genome of Azotobacter vinelandii does not include a full SUF system and thus permits the study of the effects of IscR regulation unrelated to SUF. In this study, the aim was to analyze the expression of isc operon in wild type and mutant strains of A. vinelandii IscR by the techniques of the transcriptome sequencing and qRT-PCR. The replacement of Cys92, Cys104, His107 and a deletion of 120 bp region encoding the second IscR domain led to an increased expression of the whole isc operon. It also showed a clear phenotypic difference in colonies size in the strains carrying the substitutions of His and Cys, it was smaller compared to the wild type strain. The replacement of Cys98 and Cys111, or the double substitution Cys98/111 not led to an altered operon expression. The [Fe-S] cluster binding or not, is therefore responsible for the regulation of the isc operon in A. vinelandii as well as of other operons encoding proteins involved in electron tranport chains.

Submitted by JÚLIO HEBER SILVA (julioheber@yahoo.com.br) on 2016-11-11T17:21:02Z No. of bitstreams: 2 Dissertação - Sandro Alex Helrigel Abreu - 2016.pdf: 1948362 bytes, checksum: ab3935a37704169b650d8c42e4ff1297 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Jaqueline Silva (jtas29@gmail.com) on 2016-11-17T16:16:30Z (GMT) No. of bitstreams: 2 Dissertação - Sandro Alex Helrigel Abreu - 2016.pdf: 1948362 bytes, checksum: ab3935a37704169b650d8c42e4ff1297 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-11-17T16:16:30Z (GMT). No. of bitstreams: 2 Dissertação - Sandro Alex Helrigel Abreu - 2016.pdf: 1948362 bytes, checksum: ab3935a37704169b650d8c42e4ff1297 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-03-11 / The Agroforestry Systems (SAF’s) are models of agricultural exploration that using forest species intercropped with agricultural crops and/or forage with or without animal presence. They have been widely disseminated therefore contribute to the sustainability of the agriculture. This study was developed from an experiment conducted in agrossilvicultural system during the period 2013-2015, the Federal University of Goiás, city of Goiania, GO. The objective of this study was to evaluate the chemical properties of soil, development and productivity of plant components in system integration (Teca and soybean), using different fertilization soil and cropping systems. The experimental design was a randomized block with four replications, in arrangement factorial 4 x 2, consists of four types of fertilization: no application (control); mineral fertilization; application of cattle manure and application of sewage sludge in two cropping systems: single Teca and Teca intercropped with soybeans. The chemical properties of the soil were favored by the application of sewage sludge. There not increase in levels of heavy metals in soil by use of organic waste. The productivity of soybean fertilized with sewage sludge did not differ of the mineral fertilizer, being higher other fertilization. The initial performance of Teca in single cropping was favored by the application of both organic waste. However, when intercropped with soybean, sewage sludge application resulted in higher values of height and diameter at breast height (DBH). The canopy of the tree component of the system was not influenced by the type of fertilizer used, keeping constant the light rate in the different fertilization. The use of sewage sludge is favorable both for the initial development of Teca as plants for soybean yield, being recommended in agrossilviculturals systems. / Os Sistemas Agroflorestais (SAFs) são modelos de produção agropecuária que utilizam espécies florestais consorciadas com espécies agrícolas e, ou, forrageiras com ou sem a presença animal. Têm sido amplamente divulgados, pois contribuem para a sustentabilidade da exploração agropecuária. O presente estudo foi desenvolvido a partir de um experimento conduzido em sistema agrossilvicultural durante o período de 2013 a 2015, na Universidade Federal de Goiás, município de Goiânia, GO. O seu objetivo deste estudo foi avaliar as propriedades químicas do solo, desenvolvimento e produtividade dos componentes vegetais no sistema de integração (teca e soja), com utilização de diferentes fertilizações do solo e sistemas de cultivo. O delineamento experimental foi em blocos ao acaso, com quatro repetições, em esquema fatorial 4 x 2, constituído por quatro tipos de fertilizações: nenhuma aplicação (testemunha); adubação mineral; aplicação de esterco bovino e aplicação de lodo de esgoto, em dois sistemas de cultivo: teca em nonocultivo e teca consorciada com soja. As propriedades químicas do solo foram favorecidas pela aplicação de lodo de esgoto. Não houve incremento nos níveis de elementos potencialmente tóxicos no solo pela utilização de resíduos orgânicos. A produtividade da soja adubada com lodo de esgoto não diferiu da adubada com fertilizante mineral, sendo superiores às das demais fertilizações. O desempenho inicial da teca no cultivo solteiro foi favorecido pela aplicação de ambos os resíduos orgânicos. Entretanto, quando consorciada com a soja, a aplicação de lodo de esgoto resultou em maiores valores de altura e diâmetro à altura do peito (DAP). O dossel do componente arbóreo do sistema não foi influenciado pelo tipo de adubo empregado, mantendo constante o regime de luz nas diferentes fertilizações. A utilização de lodo de esgoto apresenta-se favorável tanto para o desenvolvimento inicial de plantas de teca como para o rendimento da soja, sendo recomendada em sistemas agrossilviculturais.

Face à une demande mondiale en bois en constante augmentation, les forêts plantées sont en rapide expansion, notamment au Brésil où les plantations d'eucalyptus pourraient couvrir 10 millions d'hectares d'ici 2020. Ces plantations hautement productives soulèvent des questions importantes au niveau (i) de leur durabilité dans un contexte de changement climatique et (i) de leur impact sur l’environnement, en particulier sur les cycles de l'eau, du carbone et des nutriments. La capacité des eucalyptus à développer un système racinaire très profond (<15 m) pour atteindre la nappe phréatique, pourrait jouer un rôle clé dans l’adaptation à des disponibilités plus faible en eau. Cependant, le rôle de ces racines fines profondes dans la nutrition des plantes a jusque-là été extrêmement peu documenté.Dans ce contexte, l'objectif général de cette thèse était d'évaluer l'influence de la profondeur et de la disponibilité de l’eau sur le fonctionnement des racines fines à travers l’étude de la rhizosphère. Pour cela, une plantation clonale d’Eucalyptus grandis de 5 ans a été étudiée au Brésil sous deux régimes hydriques contrastés : un traitement + W, recevant une pluviométrie normale a été comparé à un traitement –W dans lequel 37% des pluviolessivats sont exclus. Des essais ont été réalisés dans le but d'appliquer une technologie de laboratoire innovante au champ : les optodes, permettant la cartographie du pH rhizosphérique notamment. Les rhizodepôts libérés par les racines fines d’eucalyptus interférant avec le signal du capteur optique, nous n’avons pas pu obtenir de résultats interprétables. Cependant, des tests réalisés sur le pin nous laissent confiants quant à la possibilité d'utiliser ce système, en suivant quelques recommandations. Des analyses destructives ont été réalisées sur du sol rhizosphérique et non-rhizosphérique échantillonnés le long d'un profil de 4 m. Au niveau de la nutrition : une accumulation de potassium et de protons au sein de la rhizosphère a été observée, en particulier en dessous d’1 m (x3,0 et x1,1 pour K et H3O+ en + W, resp.) et en condition de réduction des précipitations (x7,0 et x1,4 pour K et H3O+ en –W, resp.). La répétition de ces mesures pendant la saison des pluies a confirmé l'enrichissement de protons et de K dans la rhizosphère, ce qui suggère que ces processus se produisent tout au long de l'année. Cependant, l’absence d’effet traitement durant la saison des pluies laisse suggérer une bonne résilience potentielle du système. La quantité de K amenée à la surface des racines fines par flux de masse, estimée à 2 kg de K ha-1 an-1, ne permet pas d’expliquer la quantité de potassium absorbé par les arbres, estimée à 17,5 kg de K ha-1 an-1, ni l'accumulation observée dans la rhizosphère. Une explication plus probable est l'altération des minéraux potassiques induite par le fonctionnement racinaire, et notamment l’acidification. La preuve de la possibilité d’association ectomycorhiziennes jusqu'à 4 m de profondeur renforce l'hypothèse d'un rôle clé des racines fines profondes dans la nutrition des plantes. Une concentration élevée en Al3+ a aussi été mesurée au sein de la rhizosphère (jusqu'à 12 mg kg-1). Au niveau du stockage du carbone : malgré la diminution exponentielle attendue de la concentration en C et N avec la profondeur (de 0,72 à 0,12 ‰ entre 0 et 4 m), nos résultats ont montré que plus de la moitié du stock de carbone contenu dans le sol non rhizosphérique était situé en dessous d’1 m. Une accumulation de C dans la rhizosphère a été mesurée, en particulier en profondeur (x1,4 en dessous d’1 m en + W) et en condition de réduction des pluies (x3,0 à 4 m en –W). Les mêmes tendances ont été observées pour N. L’effet rhizosphérique a été conservé pendant la saison des pluies, mais pas l'effet du traitement. Ce travail a confirmé que les racines fines profondes jouent un rôle clé, pour la nutrition des plantes et le stockage de carbone, en contexte de changement climatique particulièrement. / Due to the constant increase of the world demand for wood, the planted forests are in fast expansion notably in tropical countries such as Brazil where plantations of eucalypts, the most productive and spread out planted species, may reach 10 million ha by 2020. The expansion of these plantations on less fertile sites, combined with the context of climate change lead to important issues about (i) the sustainability of these plantations under more frequent and intense drought events and (i) the impact on the environment of these highly productive plantations with very short rotations (6 yr), particularly for nutrient, water and carbon cycles. Eucalypt trees are able to develop very deep root system (<15 m) to reach the water table, and this may play a key role to cope with decreasing soil water availability. However, the role of these deep fine roots in plant nutrition is dramatically under-documented. In this context, the general objective of this study was to evaluate the influence of soil depth combined with water availability on fine root functioning through characterization of the rhizosphere properties. For this purpose, a 5-yr-old clonal Eucalyptus grandis plantation was studied in Brazil in two contrasted water regimes: the +W treatment, receiving normal rainfall was compared with the –W treatment where 37% of the throughfall were excluded in order to mimick the future climate forecasted in the region. Exploratory tests were carried out for the introduction of an innovative lab technology under field conditions: the optodes, which allow mapping rhizosphere pH. The rhizodeposition of eucalypt fine roots interfered with the optical sensor signal and prevented us to get interpretable results. However, some tests on pine trees let us confident of the possibility of using our system for field studies at depth, using some recommendations. Destructive analyses of rhizosphere and bulk soil samples collected along a 4-m deep soil profile showed an effect of depth and rainfall reduction on rhizosphere pH, potassium concentration, rhizodeposition pattern and carbon storage capacity. Concerning nutrition issues, we found an accumulation of potassium and protons within the rhizosphere, especially below 1-m depth (x3.0 and x1.1 for K and H3O+ in +W, respectively) and in reduced rainfall conditions (x7.0 and x1.4 for K and H3O+ in –W, respectively). Repeating these measurements during rainy season confirmed the enrichment of protons and potassium within the rhizosphere, suggesting that these processes may occur all along the year but no treatment effect was observed anymore, pointing to a potential good resilience of the system. The amount of K brought to fine roots by mass flow was estimated to 2.0 kg K ha-1 yr-1 and could not explain the amount of potassium taken up by trees estimated to 17.5 kg K ha-1 yr-1 and the observed accumulation in the rhizosphere. A more likely explanation was the root-induced weathering of K-bearing minerals, partly related to rhizosphere acidification. Proof of ectomycorrhizal association down to 4-m depth further supported the hypothesis of a key role of deep fine roots in plant nutrition. High exchangeable Al3+ concentration was found within the rhizosphere (up to 12.0 mg kg-1). Concerning the carbon storage issue, despite an expected exponential decrease of C and N concentrations within the bulk soil with depth (0.72‰ to 0.12‰ from top soil to 4-m depth), our results showed that more than half of soil C stock within the bulk soil occurred below the first meter. An accumulation of C within the rhizosphere was found, especially at depth (x1.4 below 1 m in +W) and in reduced rainfall conditions (x3.0 at 4-m depth in –W). The same trends were found for N. The rhizosphere effect was conserved during rainy season but not the treatment effect. This work confirmed that deep fine roots play a key role, especially in the context of climate change, for plant nutrition and carbon storage.

Orientador: Magali Ribeiro da Silva / Coorientador: Iraê Amaral Guerrini / Banca: Hélio Grassi Filho / Banca: Gisela Ferreira / Resumo: A produção de mudas da espécie Eucalyptus grandis x Eucalyptus urophylla tem crescido muito nos últimos anos no Brasil, devido a sua boa adaptação nos diferentes solos e regiões, possuindo comportamentos diferentes quanto à exigência nutricional em diferentes tipos de substrato que o mercado oferece. O conhecimento desses comportamentos trará benefícios econômicos e diminuição dos impactos ambientais causados pelo uso excessivo de fertilizantes. Neste trabalho buscou-se avaliar o efeito de doses de fósforo em três tipos de substratos na produção de mudas de Eucalyptus grandis x Eucalyptus urophylla. O experimento foi inteiramente casualizado em fatorial 3x4, utilizando 3 substratos e 4 doses de fósforo na base, totalizando 12 tratamentos distribuídos em 4 parcelas com 25 plantas. O adubo usado na fertilização de base foi o superfosfato simples e as doses foram de 0, 160, 320 e 480 g por m3 de substrato. Os substratos utilizados foram: Carolina Soil® a base de turfa, vermiculita e casca de arroz carbonizada; substrato Mecplant® a base de casca de pinus e vermiculita e substrato a base de fibra de coco e vermiculita. As avaliações do experimento constituíram-se de análise química do substrato e características morfológicas das mudas: altura da parte aérea, diâmetro do coleto, massas secas da parte aérea e radicular e qualidade de raiz. Em função dos resultados obtidos pode-se inferir que para o substrato Carolina Soil® a dose que apresentou mudas com maior desenvolvimento foi a de 320 g m-3. Para o substrato fibra de coco + vermiculita foi a de 160 g m-3 e para o substrato a Mecplant® tanto na dose zero quanto na de 480 g m-3 apresentaram resultados semelhantes, indicando a não necessidade de aplicação de P na adubação de base neste substrato. Os três substratos produziram mudas semelhantes e dentro do padrão de qualidade adequado / Abstract: The production of cuttings of the species Eucalyptus grandis x Eucalyptus urophylla has grown significantly in recent years in Brazil due to its good adaptation to different types of soil and region, having different behaviors a far as its nutritional demands on the different kinds of substrate offered by the market. Knowledge of these behaviors will bring economic benefit and a diminishing of the environmental impact caused by the excessive use of fertilizers. This investigation sought to validate the effect of doses of phosphorus on three types of substrate in the production of cuttings of Eucalyptus grandis x Eucalyptus urophylla. The experiment was entirely done on 3x4 factorial, using 3 substrates of 4 doses of phosphorous on the base, totaling 12 applications distributed among 4 parcels with 25 plants each. The fertilizer used for the base was a simple superphosphate and the doses were 0, 160, 320 and 480 g per m3 of substrate. The substrates used were: truffle based Carolina Soil®, vermiculite and carbonized rice shells, vermiculite and pinus shell based Mecplant® and coconut fiber and vermiculite substrate. Evaluations in the experiment include chemical analysis of the substrate and morphological characteristics of the cuttings: height of the airborne area, stalk diameter, dry spots on the airborne area and root and overall quality of the root. From the obtained results, it's possible to infer that for the Carolina Soil® substrate, the dosage that showed the best growth was 320 g m3. For the coconut + vermiculite substrate the best results came with 160 g m-3 and for the Mecplant® substrate, both the zero dose and the 480 g m3 showed similar results, indicating that there isn't a need for the application of P on the fertilizing of the base of this substrate. The three substrates will produce similar cuttings and within an adequate pattern of quality / Mestre

Thesis (MPhil)--Stellenbosch University, 2000. / ENGLISH ABSTRACT: A thesis undertaken to quantify genotype-by-environment interaction within Eucalyptus grandis clones growing in the eastern portion of South Africa. Thirty one sites were selected to represent the "traditional" E. grandis growing areas of South Africa. Eleven common macro- site variables and twelve common micro- site soil variables were recorded at each site. Twenty seven E. grandis clones and four E. grandis hybrid clones were then evaluated over these 31 sites. An incomplete latin square design was used to evaluate the 31 test clones, and five E. grandis controls were incorporated into the trial design to link the 31 sites. Volume production, stem form, stem defects and survival were assessed at two and five years, as well as the disease infestation of three stem cankers at five years. The analytical methods which were used to evaluate and quantify the GEl portion of the study are the analysis of variance (ANOV A), correlation analysis, and joint regression analysis (IRA) together with the analysis of co-variance (ACOV AR). The growth-site association for volume production, stem form and Endothia disease infestation were investigated using factor analysis (FA), and equations derived for the species and for the individual clones using a stepwise multiple regression approach. GEl, as evaluated through JRA, revealed that an increase in site productivity lead to a positive linear response in productivity on a clonal level, and that there was a diverging or fanning pattern among the regression lines of the clones. This tendency was also observed for both the stem form and the Endothia infestation. Hence, no significant changes in the rankings of the clones were found, and only relevant differences between the clones were found to change significantly. Juvenile-mature genetic correlations for volume production and the stem form showed moderate (rg = 0,66 and rg = 0,70) correlations between the two and the five year assessments. On a species level, rainfall was the main environmental factor responsible for volume production, while latitude was the main influence on stem form and Endothia infestation. On an individual clone basis, some micro-site soil factor interaction within the clones was found for the growth-site response models. Keywords: Eucalyptus grandis, genotype environment interaction, clones, site factors, growth-site response, ANOV A, ACOV AR, GEl, FA, JRA, / AFRIKAANSE OPSOMMING: 'n Studie is ondemeem om die genotipe-omgewingsinteraksie van Eucalyptus grandis klone, wat in die oostelike deel van Suid-Afrika groei, te kwantifiseer. Eenen- dertig groeiplekke is geselekteer om die "tradisionele" E. grandis groeiplekke in Suid-Afrika te verteenwoordig. Elf gemeenskaplike makro-groeiplek veranderlikes en twaalf gemeenskaplike mikro-groeiplek veranderlikes is by elk van die groei areas opgeteken. Sewe-en-twintig E. grandis klone en vier E. grandis basterklone is daama oor hierdie 31 groeiplekke geevalueer. 'n Onvolledige Latynse roosterontwerp is gebruik om die 31 toetsklone te evalueer en vyf kontroles is gebruik om die groeiplekke gemeenskaplik te verbind. Volume produksie, stamvorm, stamdefekte en oorlewing is op twee- en vyfjarige ouderdomme geevalueer terwyl besmetting met drie stamkankers op vyf jaar beoordeel is. Die analitiese metodes wat gebruik was om genotipeomgewingsinteraksie te evalueer en te kwantifiseer is die variansie analise (ANOYA), korrelasie analise, en gesamentlike regressie analise (JRA) tesame met ko-variansie analise (ACOY AR). Die groeiplek assosiasie vir volume produksie, stamvorm en Endothia besmetting is ondersoek deur gebruik te maak van faktor analise (FA), en vergelykings is verkry vir die spesies en individuele klone deur gebruik van 'n stapsgewyse meervoudige regressie benadering. Genotipe-omgewingsinteraksie, soos geevalueer deur JRA, wys dat 'n toename in groeiplek produktiwiteit lei tot 'n positiewe lineere reaksie in produktiwiteit op klonale vlak en dat daar 'n divergerende patroon tussen die regressielyne van die klone is. Hierdie tendens is ook vir beide die stamvorm en Endothia besmetting waargeneem. Gevolglik is nie-beduidende veranderings in die rangorde van die klone gevind en slegs reletiewe verskille tussen klone is gevind. Onvolwasse-volwasse genetiese korrelasies vir volume produksie en stamvorm toon matige korrelasies (rg =0.66 en rg =0.70) tussen die twee- en vyfjaar metings. Op 'n spesiesvlak was reenval die oorheersende omgewingsfaktor verantwoordelik vir volume produksie terwyl die breedtegraad ligging stamvorm en Endothia besmetting bemvloed het. Op individuele kloonvlak het sommige mikro-groeiplek interaksie binne klone bygedra tot die groei en groeiplek reaksie modelle. Sleutelwoorde: Eucalyptus grandis, Genotipe-omgewingsinteraksie, klone, groeiplek faktore, groeiplek reaksie, ANOY A, ACOY AR, FA, JRA

Der elektrochemische Nachweis von polycyclischen aromatischen Kohlenwasserstoffen (PAK), zu denen Anthracen und Pyren gehören, bietet eine kostengünstigere, einfachere und schnellere alternative Analysemethode als herkömmliche Methoden wie GC und HPLC. Im Vergleich zu diesen Methoden weist er jedoch nach wie vor eine geringere Empfindlichkeit auf. Einige neuere Bemühungen haben an einem Mangel an Selektivität gelitten, entweder aufgrund der elektrodenmodifizierende Schicht mit hohem Hintergrundstrom oder der Wahl eines Leitelektrolyten, der die Detektion stört. Bei dem vorliegenden Versuch wurden Pt-Pd-Nanopartikel (NPs) und MWCNTs verwendet, um eine Glaskohlenstoffelektrode (GCE) zum empfindlichen Nachweis von Anthracen und Pyren zu modifizieren. Die verwendeten NPs wurden unter Verwendung eines wässrigen Extrakts aus Blättern von E. grandis synthetisiert, einem nachhaltigen und umweltfreundlichen Syntheseweg. Durch einer Optimierung der Mengen an Pt- und Pd-Ionen im Vorläufer wurden NPs mit einer durchschnittlichen Größe von 10 nm erhalten, wobei ein Verhältnis von 1 Pt-Ion zu 3 Pd-Ionen die kleinste Größe ergab. Durch XPS wurde festgestellt, dass die Zusammensetzung der NPs von Pt2+ und Pd0 dominiert wird. Die XRD-Analyse ergab eine kristalline Natur mit einer flächenzentriert-kubischen Struktur. Die Pt-Pd-NPs bewirkten eine Erhöhung des Spitzenstroms um 94 % für Pyren, führten jedoch zu niedrigeren Spitzenströmen für Anthracen. Wenn die NPs weiter mit MWCNTs zum Nachweis von Pyren verwendet wurden, wurde eine Spitzenstromsteigerung von etwa 200 % mit einem Dynamikbereich von 66–130 μM und einer LOD von 23 μM beobachtet. Es wurde auch festgestellt, dass der elektrochemische Prozess gemischt diffusions- und adsorptionskontrolliert ist. Aufgrund des Einflusses der Adsorption musste die Akkumulationszeit im Analyseverfahren berücksichtigt werden. MWCNTs wurden beim Nachweis von Anthracen angewendet, wobei eine Erhöhung des Spitzenstroms um 74 % und eine Verringerung des Überpotentials um 53 mV beobachtet wurde. Ein dynamischer Bereich von 50–146 µM und eine LOD von 42 µM wurden bestimmt. Niedrigere Konzentrationen wurden mit einer Leitungswasserprobe gemessen, die mit Anthracen versetzt war, hauptsächlich wegen der geringen Löslichkeit von PAK in Wasser. Der Einfluss der Säurebehandlung von MWCNTs auf den Nachweis von Anthracen und Pyren wurde ebenfalls untersucht. Die Säurebehandlung ermöglichte das Laden von mehr Material ohne Ablösen der modifizierten Schicht, was zu höheren Spitzenstromverbesserungen für Anthracen (533 %) und Pyren (448 %) führte. Für Anthracen und Pyren wurden LODs von 40 µM bzw. 14 µM bestimmt, die nur geringfügig niedriger sind als die bei MWCNTs/GCE und Pt-PdNPs/MWCNTs/GCE beobachteten Werte. Der Nachweis von Anthracen wurde durch die Anwesenheit von Pyren und gewöhnlichen Ionen gestört, während die LOD für Pyren in Gegenwart von Anthracen 18 µM betrug. Es wurde festgestellt, dass die auf MWCNTs basierende elektrochemische Nachweisplattform eine bessere Reaktion auf Pyren aufweist.:Bibliographische Beschreibung i Referat i Abstract iii Zeitraum, Ort der Durchführung v Acknowledgements vi Dedication vii Table of Contents viii List of Abbreviations and Symbols xii Chapter 1 1 Introduction 1 1.1 Overview 1 1.2 Polycyclic Aromatic Hydrocarbons 2 1.3 Electrochemical Sensors 7 1.3.1 General Response Curve for Chemical Sensors 10 1.4 Carbon Nanotubes 13 1.5 Use of Nanoparticles in Electrochemical Detection 18 1.6 Green Synthesis of Nanoparticles and The Rationale Behind It 21 1.7 Previous Efforts in the Electrochemical Detection of Polycyclic Aromatic Hydrocarbons 24 1.8 Objectives of the Study 26 Chapter 2 28 Experimental 28 2.1 Chemicals 28 2.1.1 Preparation of Anthracene and Pyrene Solutions 28 2.2 Collection and Preparation of Plant Material 29 2.3 Synthesis and Preparation of Materials 29 2.3.1 Synthesis of Metallic Nanoparticles 29 2.3.2 Acid Treatment of Multi-walled Carbon Nanotubes 30 2.4 Characterization of the Nanomaterials 30 2.4.1 UV-Vis Spectrophotometry 30 2.4.2 SEM/EDX and TEM Analysis 30 2.4.3 Powder X-ray Diffractometry 31 2.4.4 XPS Analysis 31 2.5 Electrochemical Measurements 31 2.5.1 Preparation of the Bare and Modified Glassy Carbon Electrode 32 2.5.2 Characterization of the Bare and the Modified Glassy Carbon Electrode 33 2.5.3 Electrocatalytic Oxidation of Anthracene on the Bare and Modified GCEs 33 2.5.4 Electrocatalytic Oxidation of Pyrene on the Bare and Modified GCEs 34 Chapter 3 35 Synthesis, Characterization, and Application of Pt-Pd Nanoparticles in the Electrochemical Detection of Anthracene and Pyrene 35 3.1 Test for Flavonoids and Polyphenols in the E. grandis Leaves’ Extract 35 3.2 Synthesis of Nanoparticles 35 3.3 Characterization of Nanoparticles 37 3.3.1 TEM Analysis 37 3.3.2 SEM Analysis 40 3.3.3 EDX Analysis 41 3.3.4 Powder X-Ray Diffraction Analysis 45 3.3.5 XPS Analysis of Pt-Pd Particles 46 3.4 Impedance Measurements of the Bare and Nanoparticle-modified Glassy Carbon Electrode 49 3.5 Electrochemical Oxidation of Anthracene and Pyrene at the Bare and Nanoparticles-modified Glassy Carbon Electrode 51 3.6 Conclusions 53 Chapter 4 55 Pt-PdNPs/MWCNTs-Modified GCE for the Detection of Pyrene 55 4.1 Impedance Measurement with Pt-PdNPs/MWCNTs/GCE 55 4.2 Electrochemical Oxidation of Pyrene on Pt-PdNPs/MWCNTs/GCE 56 4.3 Analysis of Varying Concentrations of Pyrene on Pt-PdNPs/MWCNTs/GCE 59 4.4 Selectivity 61 4.5 Conclusions 62 Chapter 5 64 Exploring Multi-walled Carbon Nanotubes for the Detection of Anthracene 64 5.1 Impedance Measurement of MWCNT-Modified Glassy Carbon Electrode 64 5.2 Electrochemical Oxidation of Anthracene on MWCNT/GCE 65 5.3 Analysis of Varying Concentrations of Anthracene Using MWCNTs/GCE 68 5.4 Detection of Anthracene in Tap Water 71 5.5 Conclusions 72 Chapter 6 73 Effect of Acid Treatment of Multi-walled Carbon Nanotubes on the Detection of Anthracene and Pyrene 73 6.1 Characterization of fMWCNTs 74 6.2 Electrochemical Oxidation of Anthracene on fMWCNTs/GCE 75 6.2.1 Effect of Change in Scan Rate 76 6.2.2 Effect of Accumulation Time 77 6.2.3 Application of fMWCNTs/GCE in the Analysis of Varying Concentrations of Anthracene 77 6.3 Electrochemical Oxidation of Pyrene on fMWCNTs/GCE 79 6.4 Selectivity 82 6.4.1 Co-detection of Anthracene and Pyrene at fMWCNTs/GCE 83 6.4.2 Interference of Some Common Ions 85 6.5 Detection of Pyrene in Tapwater using fMWCNTs/GCE 86 6.6 Conclusions 87 Chapter 7 88 Summary and Outlook 88 7.1 Summary 88 7.2 Outlook 90 References 92 Selbständigkeitserklärung 101 Curriculum Vitae 102 / Electrochemical detection of polycyclic aromatic hydrocarbons (PAHs), which include anthracene and pyrene, offers a cheaper, simpler, and faster alternative method of analysis than conventional methods like GC and HPLC. However, it still is not as sensitive as these methods. Some recent efforts have suffered from lack of selectivity, either from the electrode modifying layer having high background current or from the choice of supporting electrolyte interfering with the detection. In this work, Pt-Pd nanoparticles (NPs) and MWCNTs were used to modify a glassy carbon electrode (GCE) for sensitive detection of anthracene and pyrene. The NPs used were synthesized using an aqueous extract from E. grandis leaves, a sustainable and environmentally friendly synthetic route. NPs with an average size of 10 nm were obtained by optimizing the amounts of Pt- and Pd-ions in the precursor, with a ratio of 1:3 Pt to Pd-ions producing the smallest size. Through XPS, the composition of the NPs was established to be dominated by Pt2+ and Pd0. XRD analysis revealed a crystalline nature with a face-centered cubic structure. The Pt-Pd NPs produced 94 % enhancement in the peak current for pyrene but resulted in lower peak currents for anthracene. When the NPs were further used with MWCNTs for the detection of pyrene, about 200% peak current enhancement was observed with a dynamic range of 66–130 µM and LOD of 23 µM. The electrochemical process was also established to be mixed diffusion- and adsorption-controlled. The influence of adsorption necessitated the employment of accumulation time in the analysis procedure. MWCNTs were applied in the detection of anthracene and a 74 % peak current enhancement and a reduction in the overpotential by 53 mV were observed. A dynamic range of 50–146 µM and LOD of 42 µM were determined. Lower concentrations were recovered from a tap water sample that was spiked with anthracene, mainly because of the low solubility of PAHs in water. Effect of acid treatment of MWCNTs on the detection of anthracene and pyrene was also investigated. Acid treatment allowed for loading of more material without peeling off of the modified layer which resulted in higher peak current enhancements for anthracene (533%) and pyrene (448%). LODs of 40 µM and 14 µM were determined for anthracene and pyrene respectively, which are only slightly lower than what was observed at MWCNTs/GCE and Pt-PdNPs/MWCNTs/GCE. Detection of anthracene was interfered by the presence of pyrene and common ions, while the LOD for pyrene in the presence of anthracene was 18 µM. The MWCNTs based electrochemical detection platform was found to have a better response towards pyrene.:Bibliographische Beschreibung i Referat i Abstract iii Zeitraum, Ort der Durchführung v Acknowledgements vi Dedication vii Table of Contents viii List of Abbreviations and Symbols xii Chapter 1 1 Introduction 1 1.1 Overview 1 1.2 Polycyclic Aromatic Hydrocarbons 2 1.3 Electrochemical Sensors 7 1.3.1 General Response Curve for Chemical Sensors 10 1.4 Carbon Nanotubes 13 1.5 Use of Nanoparticles in Electrochemical Detection 18 1.6 Green Synthesis of Nanoparticles and The Rationale Behind It 21 1.7 Previous Efforts in the Electrochemical Detection of Polycyclic Aromatic Hydrocarbons 24 1.8 Objectives of the Study 26 Chapter 2 28 Experimental 28 2.1 Chemicals 28 2.1.1 Preparation of Anthracene and Pyrene Solutions 28 2.2 Collection and Preparation of Plant Material 29 2.3 Synthesis and Preparation of Materials 29 2.3.1 Synthesis of Metallic Nanoparticles 29 2.3.2 Acid Treatment of Multi-walled Carbon Nanotubes 30 2.4 Characterization of the Nanomaterials 30 2.4.1 UV-Vis Spectrophotometry 30 2.4.2 SEM/EDX and TEM Analysis 30 2.4.3 Powder X-ray Diffractometry 31 2.4.4 XPS Analysis 31 2.5 Electrochemical Measurements 31 2.5.1 Preparation of the Bare and Modified Glassy Carbon Electrode 32 2.5.2 Characterization of the Bare and the Modified Glassy Carbon Electrode 33 2.5.3 Electrocatalytic Oxidation of Anthracene on the Bare and Modified GCEs 33 2.5.4 Electrocatalytic Oxidation of Pyrene on the Bare and Modified GCEs 34 Chapter 3 35 Synthesis, Characterization, and Application of Pt-Pd Nanoparticles in the Electrochemical Detection of Anthracene and Pyrene 35 3.1 Test for Flavonoids and Polyphenols in the E. grandis Leaves’ Extract 35 3.2 Synthesis of Nanoparticles 35 3.3 Characterization of Nanoparticles 37 3.3.1 TEM Analysis 37 3.3.2 SEM Analysis 40 3.3.3 EDX Analysis 41 3.3.4 Powder X-Ray Diffraction Analysis 45 3.3.5 XPS Analysis of Pt-Pd Particles 46 3.4 Impedance Measurements of the Bare and Nanoparticle-modified Glassy Carbon Electrode 49 3.5 Electrochemical Oxidation of Anthracene and Pyrene at the Bare and Nanoparticles-modified Glassy Carbon Electrode 51 3.6 Conclusions 53 Chapter 4 55 Pt-PdNPs/MWCNTs-Modified GCE for the Detection of Pyrene 55 4.1 Impedance Measurement with Pt-PdNPs/MWCNTs/GCE 55 4.2 Electrochemical Oxidation of Pyrene on Pt-PdNPs/MWCNTs/GCE 56 4.3 Analysis of Varying Concentrations of Pyrene on Pt-PdNPs/MWCNTs/GCE 59 4.4 Selectivity 61 4.5 Conclusions 62 Chapter 5 64 Exploring Multi-walled Carbon Nanotubes for the Detection of Anthracene 64 5.1 Impedance Measurement of MWCNT-Modified Glassy Carbon Electrode 64 5.2 Electrochemical Oxidation of Anthracene on MWCNT/GCE 65 5.3 Analysis of Varying Concentrations of Anthracene Using MWCNTs/GCE 68 5.4 Detection of Anthracene in Tap Water 71 5.5 Conclusions 72 Chapter 6 73 Effect of Acid Treatment of Multi-walled Carbon Nanotubes on the Detection of Anthracene and Pyrene 73 6.1 Characterization of fMWCNTs 74 6.2 Electrochemical Oxidation of Anthracene on fMWCNTs/GCE 75 6.2.1 Effect of Change in Scan Rate 76 6.2.2 Effect of Accumulation Time 77 6.2.3 Application of fMWCNTs/GCE in the Analysis of Varying Concentrations of Anthracene 77 6.3 Electrochemical Oxidation of Pyrene on fMWCNTs/GCE 79 6.4 Selectivity 82 6.4.1 Co-detection of Anthracene and Pyrene at fMWCNTs/GCE 83 6.4.2 Interference of Some Common Ions 85 6.5 Detection of Pyrene in Tapwater using fMWCNTs/GCE 86 6.6 Conclusions 87 Chapter 7 88 Summary and Outlook 88 7.1 Summary 88 7.2 Outlook 90 References 92 Selbständigkeitserklärung 101 Curriculum Vitae 102

Thesis (PhD (For))--Stellenbosch University, 2012. / ENGLISH ABSTRACT: A primary reason for the existence of the forest industry is to provide a renewable and natural resource for much needed timber and fibre products. Substantial improvements in management practices are required to increase forest volume and pulp yields for increased demand. Eucalyptus grandis clonal trees of age 6.75 years, grown in a Nelder 1a spacing experiment, were sampled and analysed to describe the effect of planting density on i) growth and yield, ii) wood properties and iii) pulp and paper quality. The main objective was to populate a fibre productivity index (FPI) which would be suitable from technical and economical perspectives. A material study was conducted on the wood and in addition, two methods were developed to further describe the variability of the forest resource to i) separate growth rings by means of wood density peaks from gamma-ray densitometry and ii) calibrate near infrared (NIR) prediction models. The results indicated that planting density did not influence the variability of wood density but mechanisms affecting available soil water are important. NIR prediction models were developed to rapidly and reliably assess wood properties on a non-destructive basis. The validation models for wood density, total pulp yield, kappa number and insoluble lignin returned high predictive ability. When applied to predict chemical properties from an independent data set, the outcomes were accurate in comparison with measured data. Growth and yield functions were developed for tree survival, dominant height and basal area. They accurately predicted outcomes as demonstrated by the goodness of fit and their logical behaviour tested over the range of planting densities. When the most extreme stand density treatments, 6809 and 275 trees per hectare (TPH) were evaluated for wood and fibre properties, the larger trees grown at 275 TPH, produced wood of better quality for pulp processing; basic wood density at 0.520 g cm–3 (21 % higher), fibre cell wall thickness at 2.10 μm (18.6 % thicker) and fibre lumen diameter at 8.16 μm (9.9 % lower) than for 6809 TPH. Intra-specific tree variability of wood and product properties increased from diameter at breast height (DBH) to 35 % and then decreased to 65 % of tree height. The effect of planting density was carried throughout the product value chain up to the paper manufacturing phase. Paper with higher bulk mass and thickness and more porous sheets is most likely to be made from lower planting densities (801 and 275 TPH), and stronger, smoother and denser paper is most likely to be made with trees at high planting densities (6809 or 2336 TPH). From the growth and yield and materials investigation, technical indicators identified to populate a fibre productivity index were: i) mean annual increment (MAI) as a forestry growth indicator, ii) wood density, summarising the composition of wood and, iii) pulp yield, the indicator of the amount of fibre processed through a chemical cooking process. Delivered cost of timber to the mill, was identified as the most suitable economic indicator which included fixed costs elements, variable costs and aspects of mill efficiency. The product of the technical and economic indicators concluded in a profit/loss scenario of producing 1 ton of pulp was deemed the best index to describe the entire and integrated value chain. This index, termed the Fibre Productivity Index (FPI) at the Mill, denoted as FPMill, is an integrated index that is easy to interpret in the realms of a forestry - pulp manufacturing, and can be used for differential pricing of timber for wood quality. / AFRIKAANSE OPSOMMING: 'n Primêre rede vir die bestaan van die bosbouindustrie is om ‘n hernubare, natuurlike hulpbron vir hout en vesel te voorsien. Aansienlike verbeterings in bestuurspraktyke is nodig om die houtvolume en pulpopbrengste vir die toename in aanvraag te verhoog. Eucalyptus grandis klonale bome met ‘n ouderdom van 6.75 jaar en wat in 'n Nelder 1a spasiëring eksperiment gegroei is, is versamel en ontleed om die effek van opstandsdigtheid te beskryf op a) groei en opbrengs, b) houteienskappe en c) pulp- en papiergehalte. Die hoofdoel was om 'n veselproduktiwiteitsindeks (FPI), wat geskik sou wees in terme van tegniese en ekonomiese perspektiewe, te ontwikkel. 'n Materiaalkundigestudie is op hout uitgevoer. Twee metodes is ontwikkel om die variasie in hout as natuurlike hulpbron te beskryf deur a) vroeëhout- en laathoutdigtheidspieke deur gammastraal-densitometrie van mekaar te skei en variasie in groeiringe te beskryf en b) daarstelling van naby-infrarooispektroskopiese (NIR) voorspellingsmodelle. Die resultate het aangedui dat aanplantingsdigtheid nie ‘n invloed het op die variasie van houtdigtheid nie, maar dat meganismes wat beskikbare grondwater bepaal, belangrik is. NIR-voorspellingsmodelle is ontwikkel om houteienskappe op 'n nie-destruktiewe manier betroubaar te kan evalueer. Die validasiemodelle vir houtdigtheid, pulpopbrengs, kappanommer en onoplosbare lignien, openbaar akkurate voorspellingsvermoë. Wanneer dit toegepas word om chemiese eienskappe van 'n onafhanklike datastel te voorspel, was die resultate akkuraat in vergelyking met gemete data. Groei- en opbrengsfunksies is ontwikkel vir mortaliteit, dominante boomhoogte en basale area. Akkurate voorspellingsuitkomste is verkry soos gedemonstreer deur die logiese gedrag wat getoets is vir alle plantdigthede. Toe die mees ekstreme opstansdigtheidbehandelings vir hul hout- en veseleienskappe geëvalueer is, was die hout van die groter bome, teen 275 stamme per hektaar (SPH), van beter gehalte. Dit was veral prominent vir houtdigtheid van 0.520 g cm-3 (21 % hoër), veselselwanddikte van 2.10 μm (18.6 % dikker) en vesellumendeursnit van 8.16 μm (9.9 % laer) as by die hoër (6809) SPH. Intra-spesifieke boomvariasie van hout- en produkeienskappe het toegeneem van deursnee op borshoogte (DBH) tot 35 % en dan weer afgeneem tot 65 % van die boomhoogte. Die effek van plantdigtheid is regdeur die produkwaardeketting tot by die papiervervaardigingstadium sigbaar. Papier met hoër basismassa en dikte, en meer poreuse papiervelle kan meer waarskynlik van laer aanplantdigtheid (801 en 275 TPH) bome gemaak kan word. Papier wat sterker, gladder en digter is, kan waarskynlik gemaak word van hout van bome teen hoë aanplantdigthede (6809 of 2336 SPH). Die veselproduktiwiteitindeks wat ontwikkel is uit die materiaalondersoek en tegniese aanwysers wat geïdentifiseer is sluit in i) gemiddelde jaarlikse aanwas, as 'n bosbou groei-indikator, ii) houtdigtheid, wat ‘n opsomming van die samestelling van hout is, en iii) pulpopbrengs; die aanduiding van die hoeveelheid vesel verwerk deur 'n chemiese verpulpingsproses. Gelewerde koste van hout by die pulpmeul is geïdentifiseer as die mees geskikte ekonomiese aanwyser wat vaste kosteelemente, veranderlike koste en aspekte van die meul se doeltreffendheid insluit. Die produk van die tegniese en ekonomiese aanwysers is saamgevat in 'n wins / verlies opsie vir die vervaardiging van 1 ton pulp, en is beskou as die mees geskikte indeks om die geïntegreerde waardeketting te beskryf. Dié indeks, die sogenaamde Vesel Produktiwiteitsindeks (VPI) by die Pulpmeul, aangedui as VPMeul, is 'n geïntegreerde indeks wat maklik is om te interpreteer in 'n bosbou - pulpvervaardigingsopset, en kan gebruik word in die differensiële prysbepaling van hout waarby die kwaliteit in ag geneem word.