Made available in DSpace on 2014-08-20T14:36:55Z (GMT). No. of bitstreams: 1 Dissertacao_ Monica_ Peters.pdf: 878946 bytes, checksum: b7413c46a3fb8157f851699145fb57ab (MD5) Previous issue date: 2006-04-07 / The organic substance degradation in flooded soil produces organic compouds that can be toxic to the rice plants. The acetic acid is the principal intermediate product from anaerobic degradation in flooded soil. Among several factors that intervene in toxicity of organic acid, pH show to be the most important. The increment of pH induced on increase on dissociated form of acid that is less toxic. So, it is possible that calcium disposed affect the toxicity produced by organic acid. Therefore, the calcium offers stability to the cell membranes by linking among phosphates and carboxilics group of phospholipids, and proteins. The work objective was to estimate the effect of different pH values and calcium concentrations in nutritional solution on toxicity of acetic acid on rice. Two experiments were lead in laboratory with artificial light supplied. The treatments of experiment one were: pH nutritional solution (3.7; 4.7; 5.7 and 6.7) and acetic acid (zero and 2.5 mM of acid). The treatments of experiment two were: calcium concentrations (0.2; 1.0 and 5.0 mM) and acetic acid (zero and 2.5 mM of acid). The morphologic parameters radicular system (total length, radius, area, root dry weight and growth of main root ), shoot dry weight, shoot stature and the concentration and total accumulated amount of N, P, K, Ca and Mg in plants were evaluated. The data of experiment one were submitted to variance analysis, average to Duncan s test 5% probability and polynomial regression analysis and in the experiment two to variance analysis and the average to Duncan s test 5% probability using the statistical program Winstat. The increment on pH values of nutritional solution on presence of acetic acid increased the radicular system and shoot. It also increased the N concentration in shoot of rice. The growth on rice plants were not affected by calcium concentrations in nutritional solution on presence of acetic acid. / A decomposição da matéria orgânica em solos alagados produz compostos orgânicos que podem ser tóxicos às plantas de arroz. O ácido acético é o principal produto intermediário da decomposição anaeróbia da matéria orgânica nos solos alagados. Dentre muitos fatores que interferem na toxidez dos ácidos orgânicos o pH é um fator importante. O aumento deste leva ao acréscimo na proporção da forma dissociada do ácido, que apresenta menor toxidez. Acredita-se na hipótese de que o teor de cálcio no tecido das plantas também possa influenciar na toxidez por ácidos orgânicos. O cálcio oferece estabilidade às membranas das células pela ligação entre fosfatos e grupos carboxílicos de fosfolipídio e proteínas na superfície das membranas. Com base nisto, o objetivo deste trabalho foi avaliar os efeitos de diferentes valores de pH e concentrações de cálcio em solução nutritiva sobre a toxidez por ácido acético em plantas de arroz. Para isto, foram realizados dois experimentos em bancada de laboratório com fornecimento de luz artificial. Os tratamentos do experimento 1 foram: pH da solução nutritiva (3,7; 4,7; 5,7; 6,7) e ácido acético (0,0 e 2,5 mM), com 3 repetições. Os tratamentos do experimento 2 foram: doses de cálcio (0,2; 1,0; 5,0 mM) e ácido acético (0,0 e 2,5mM), com 4 repetições. Os indicadores avaliados nos dois experimentos foram: parâmetros morfológicos (comprimento total, raio, área, peso de matéria seca radicular e crescimento da raiz principal) do sistema radicular, altura de plantas e peso de matéria seca da parte aérea e concentração e quantidade total acumulada de N, P, K, Ca e Mg na parte aérea das plantas. Os dados obtidos no experimento 1 foram submetidos à análise da variância, teste de Duncan a 5% de probabilidade e análise de regressão polinomial e no experimento 2 análise de variância e teste de Duncan a 5% de probabilidade utilizando o programa estatístico Winstat. O incremento nos valores de pH na solução nutritiva na presença do ácido acético aumentou o desenvolvimento do sistema radicular e da parte aérea das plantas. Também aumentou a concentração de N na parte aérea do arroz. A presença de diferentes concentrações de cálcio na solução nutritiva não afetou a toxidez pelo ácido acético nas plantas de arroz. Palavras-chave:

Demand for lithium (Li) and cobalt (Co) is on the rise, due in part to their increased use in rechargeable Li-ion batteries (RLIB). Current recycling processes that utilize chemical leaching efficiently recover in Li and Co from the cathode material in spent batteries; however, these processes are costly and emit hazardous waste into the environment. Therefore, a more sustainable process for recycling Li and Co is needed, and bioleaching may provide a solution. Fungal bioleaching has been shown in previous studies to effectively mobilize metals (Pb, Al, Mn, Cu, and Zn) from mine tailings, electronic scrap, and spent batteries with organic acids. However, little is known regarding fungal tolerance to Li and Co, and if the concentrations of organic acids excreted by fungi can effectively leach Li and Co from the cathode material. In order to address these questions, experiments were first conducted to test the Li and Co leaching efficiency with organic acids at concentrations similar to what has been previously reported in fungal cultures. The remaining experiments were performed with three fungal species: Aspergillus niger, Penicillium chrysogenum, and Penicillium simplicissimum. First, fungal biomass production, pH and organic acid excretion were examined when the fungi were grown in Czapek dox broth (CDB) or Sabouraud dextrose broth (SDB). Second, fungal biomass production and pH were examined when the fungi were grown in the presence of Li or Co. This determines tolerance of the fungi to the metals, and if fungal processes were inhibited by the metals. Third, bioleaching was performed with cathode material from RLIB in batch cultures to test the ability of organic acids excreted by A. niger to mobilize Li and Co. Three bioleaching strategies, one-step, two-step, and spent-medium leaching techniques were used to mobilize Li and Co from the cathode in RLIB. Low concentrations of organic acids similar to what is excreted by fungi have not been tested to leach Li and Co from the cathode in RLIB. Results from chemical leaching with low concentrations of organic acids in this study indicate that organic acid leaching efficiency can be increased by utilizing higher concentrations (above 50 mM) of citric or oxalic acid to mobilize Li or Co from the cathode in RLIB. Furthermore, 100 mM of citric acid or 100 mM of oxalic acid mobilized more Co or Li than mixtures of organic acids. Notably the addition of hydrogen peroxide to mixed concentrations of organic acids significantly improved mobilization of Li and Co under abiotic conditions. Different growth media may alter biomass production and potentially organic acid excretion by the three fungal species. Analysis of biomass production by A. niger and P. simplicissimum showed that differences in media composition between CDB and SDB did not affect collected biomass for each species. However, CDB cultures with P. chrysogenum had significantly less biomass than SDB cultures after 10 days of growth. Differences in growth by P. chrysogenum between CDB and SDB may be attributed to preferred nutrients and/or low pH present in SDB cultures. Biomass production by the three fungi increased up to day 10 in CDB or SDB. This result indicated that nutrients in CDB or SDB were not limiting toward fungal growth. Cultures with A. niger had the highest concentrations of organic acids (50 mM of oxalic acid), followed by cultures with P. simplicissimum (30 mM oxalic acid), and P. chrysogenum (less than 5 mM oxalic acid). Organic acids excreted by all three fungal species were detected in cultures in CDB, while only A. niger and P. chrysogenum excreted organic acids in SDB cultures. Metals such a Li or Co present in the cathode of RLIB may be toxic to fungal processes when exposed to high metal concentrations. Metal tolerance experiments indicate that biomass production by the three fungi was significantly inhibited by 100 mg/L Co compared to controls, which contained no metal. Li at a concentration of 1000 mg/L inhibited biomass production by A. niger and P. simplicissimum. However, biomass production by P. chrysogenum was not significantly inhibited by 1000 mg/L Li. I found that P. simplicissimum was the most susceptible to toxic effects of Li and Co among the three fungi. In A. niger cultures amended with 100 mg/L Li or Co, pH at day 5 was similar to control cultures of A. niger without metals (pH 3.0 – 3.4), whereas pH was significantly higher in cultures with 1000 mg/L of Li or Co (pH 7.1 – 7.3). Cultures of A. niger were exposed to the cathode material from RLIB to test the leaching efficiency of excreted organic acids after mobilizing Li and Co. In bioleaching experiments with A. niger, organic acids excreted in the presence of cathode material from RLIB were quantified at concentrations under 50 mM. At the end of bioleaching experiments with A. niger, 40 mM tartaric acid was detected and was the highest produced organic acid in bioleaching cultures. However, with conditions set in this study, organic acids excreted by A. niger mobilized only ̴7% of Co and 20% of Li when using spent medium with cathode material from RLIB. According to findings in chemical leaching experiments, concentrations of organic acids higher than 50 mM will be required in fungal cultures to increase mobilization of Li or Co from the cathode material in RLIB. Modifying growth media to include higher concentrations of sucrose will potentially increase organic acid excretion as demonstrated in previous publications. Future studies should focus on how to maximize organic acid excretion by fungi when exposed to metals found in the cathode of RLIB.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The potassium (K) of a given soil depends primarily on its parent material. The K in the soil can be conceptually divided into: structural K, non-exchangeable K, exchangeable K, and K in the solution. Studies have shown that organic acids, which occur in the rhizosphere of plants and soil microorganisms can facilitate the mineral weathering with the formation of organometallic complexes. The availability of K is an important factor of the productivity for crops and their dynamics in the soil is closely related to its mineralogy. Organic acids of low molecular weight have been used in kinetic studies to release K in soils. The purpose of this study was to (a) evaluate the dynamics of K release in the presence of oxalic acid (OA) in three subtropical Alisols, (b) consider the mineralogical changes caused by soil contact with the acid, and (c) to quantify reserve K existing in three size fractions (sand, silt and clay). Samples of three Alisols of Rio Grande do Sul (RS) were collected. The fractions were separated, and burning organic matter. Furthermore, we determined the levels of K in solution, available K, exchangeable K, non-exchangeable K and total K in each fraction and the fine earth fraction (TFSA). The fractions were subjected to the dynamics of K release test, X-ray analyzes being performed before and after these procedures. PBAC1 and PBAC2 had the highest K total reserve and also the greatest content released during the dynamic test than the PVD. In the XRD patterns were identified quartz and feldspar in the sand and silt fractions. The dominant clay smectite, illite, kaolinite, disordered kaolinite, quartz, microcline, albite and magnetite were identified. No significant differences were observed in mineralogy after contact with the OA. The PBAC1 and PBAC2 soils had the greatest capacity to supply the structural K. The clay fraction of the three soils was the fraction that contributed with provision of K, but the silt fraction of the PBAC2 also released large amount of K. / O teor de potássio (K) de um determinado solo depende principalmente do seu material de origem. O K presente no solo pode ser conceitualmente dividido em: K estrutural, K não trocável, K trocável, e K na solução. Estudos comprovam que ácidos orgânicos, que ocorrem na rizosfera das plantas e microrganismos do solo, podem facilitar a intemperização dos minerais com a formação de complexos organometálicos. A disponibilidade de K é um importante fator de produtividade para as culturas e a sua dinâmica no solo está intimamente ligada à mineralogia dos solos. Ácidos orgânicos de baixo peso molecular têm sido utilizados em estudos de cinética de liberação de K em solos. O objetivo foi (a) avaliar a dinâmica de liberação de K na presença de ácido oxálico (AO) em três Argissolos subtropicais, (b) ponderar as alterações mineralógicas provocadas pelo contato do solo com o ácido, e (c) quantificar a reserva de K existente nas três frações granulométricas (areia, silte e argila). Foram coletadas amostras de três Argissolos do Rio Grande do Sul (RS). As frações granulométricas foram separadas, e a matéria orgânica queimada. Além disso, foram determinados os teores de K na solução, K disponível, K trocável, K não trocável e K total em cada fração e na fração terra fina (TFSA). As frações foram submetidas ao teste de dinâmica de liberação de K, sendo realizadas análises de Raios-X em antes e após estes procedimentos. PBAC1(Argissolo Bruno-Acinzentado Alítico típico - siltito) e PBAC2 (Argissolo Bruno-Acinzentado Alítico típico - arenito) apresentaram a maior reserva total de K e também o maior teor liberado durante o teste de dinâmica que o PVd (Argissolo Vermelho Distrófico típico - granito). Nos difratogramas foram identificados quartzo e feldspato potássico nas frações areia e silte. Na fração argila foram identificados esmectita, ilita, caulinita, caulinita desordenada, quartzo, microclínio, albita e magnetita. Não foram observadas diferenças significativas na mineralogia após o contato com o AO. Os solos PBAC1 e PBAC2 apresentaram a maior capacidade de fornecimento de K estrutural. A fração argila dos três solos foi a fração que mais contribuiu com fornecimento de K, porém a fração silte de PBAC2 destacou-se dentre as demais, apresentando também grande importância na sua liberação.

The research reported here is a study of detector systems to determine those most suited for simultaneous organic acid, inorganic anion determination. Comparisons are made on the basis of detection limits and sensitivities for conductivity, UV/Vis, photoconductivity, and derivative conductivity detection systems. The investigation was made using a constant chromatographic system with the only variable component being the detector system. Eluant optimization conditions for each detector are reported along with tables reporting detection limits and sensitivities for each detector system. Various chromatograms are also shown to provide a visual comparison between detector results.

CONTEXTE GENERAL: En raison des activités anthropiques, les sols sont souvent contaminés par des métaux lourds et des hydrocarbures pétroliers. Le nombre important de sites multi-contaminés dans l'environnement met en lumière la nécessité de trouver des solutions adéquates à ces scénarios complexes d'assainissement, qui, de plus, sont rarement étudiés. Parmi les techniques d'assainissement biologique, la phytoremédiation est une technique qui se base sur les propriétés naturelles des plantes pour assainir les sols. L'utilisation conjointe des plantes et des microorganismes pour dépolluer les sols multi-contaminés est une stratégie de traitement en plein essor. Cependant, l'obstacle majeur qui entrave la réussite de tels traitements est la faible biodisponibilité des polluants dans le sol. Par conséquent, la phytoremédiation peut être assistée par des traitements chimiques et/ou biologiques afin de surmonter cette limitation et d'améliorer l'efficacité de l'assainissement. Dans cette étude, l'approche chimique implique l'ajout d'amendements biodégradables. Enfin, la stratégie biologique retenue dans ce travail est la bioaugmentation qui consiste à ajouter dans le sol des bactéries capables d'améliorer l'assainissement des polluants et/ou favoriser la croissance des plantes. PRINCIPAUX OBJECTIFS: a) Étudier le potentiel de la luzerne pour la phytoremédiation des sols multi-contaminés, b) Étudier les effets de l'acide organique de faible poids moléculaire acide citrique et le tensioactif Tween® 80 sur le processus de phytoremédiation et c) Étudier l'effet de la bioaugmentation avec la bactérie Pseudomonas aeruginosa sur le processus de phytoremédiation. METHODES: Détermination des taux de germination et de mortalité, évaluation des paramètres physiologiques des plantes. Quantification de la biomasse végétale, des métaux lourds dans les plantes, hydrocarbures pétroliers totaux (HCT) dans le sol, et indicateurs microbiologiques du sol. Calcul des paramètres de phytoremediation.RESULTATS REMARQUABLES: La luzerne a présenté une faible tolérance aux HCT du sol à 8400 mg kg-1 de matière sèche (MS). Celle-ci qui a été améliorée lorsque les HCT étaient présents à plus faible concentration (3600 mg kg-1 MS). La luzerne a été en mesure de prendre les métaux dans une proportion limitée (<100 mg kg-1 MS), tandis qu'elle a eu un effet positif sur le nombre de microorganismes du sol capables de dégrader les alcanes et sur l'activité de la lipase dans la rhizosphère. En outre, l'application combinée de l'acide citrique et du Tween® 80 a donné lieu à une amélioration plus importante de nombre et de l'activité microbienne dans la rhizosphère. La bioaugmentation avec P. aeruginosa a eu un effet sur l'amélioration de la biomasse de luzerne (augmentation de la biomasse végétale sèche totale de 71%). En outre, les taux les plus élevés d'élimination des HCT (68%, après 90 jours d'expérience) ont été obtenues dans les sols plantés avec la luzerne et bioaugmentées par P. aeruginosa. CONCLUSION GENERALE: La luzerne pourrait tolérer le sol co-contaminé par des métaux lourds et des hydrocarbures pétroliers, ce qui est une caractéristique essentielle en phytoremédiation. La luzerne ne peut cependant pas être considérée comme une espèce capable d'extraire activement les métaux lourds, même en présence d'amendements chimiques ou par bioaugmentation. Néanmoins, l'augmentation du nombre et de l'activité microbienne dans la rhizosphère a confirmé le potentiel de cette plante à être utilisée avec succès dans le traitement des hydrocarbures pétroliers. Ces effets ont été par ailleurs renforcés par l'application conjointe d'acide citrique et de Tween® 80. Enfin, la combinaison de la phytoremédiation et de la bioaugmentation semble une approche prometteuse pour réaliser l'assainissement des hydrocarbures pétroliers, lorsqu'ils sont présents dans des sols multi-contaminés / GENERAL BACKGROUND : As a result of anthropogenic activities, soil resources remain contaminated with heavy metals and petroleum hydrocarbons. The high frequency of occurrence of multi-contaminated soils in the environment brings to light the necessity to find remediation solutions adequate in such complex scenarios, which besides have seldom been studied. Phytoremediation is a biologically based remediation technology, which takes advantage of the intrinsic physiological abilities of plants to remediate contaminated media. Plants and their associated microorganisms perform phytoremediation processes (e.g. phytoextraction and rhizodegradation), which can bring about the clean-up of multi-contaminated soils. However, a major constraint which hinders the success of phytotechnologies is low bioavailability of pollutants in soil. As a result, chemically- and biologically-assisted phytoremediation are possible strategies used to overcome this limitation and improve the remediation efficiency. The chemical approach presented in this study involves the addition of biodegradable soil amendments to increase the ability of contaminants to be transferred from a soil compartment to plants and microorganisms. The biological strategy explored herein consists of inoculating contaminated soils with bacteria (bioaugmentation) able to improve remediation of pollutants and/or promote plant features.MAIN OBJECTIVES: a) To investigate the phytoremediation potential of alfalfa (Medicago sativa) in multi-contaminated soils b) To study the effects of the low molecular weight organic acid citric acid and the surfactant Tween® 80 on the phytoremediation process c) To assist phytoremediation with a bioaugmentation approach using Pseudomonas aeruginosa bacteria. METHODOLOGIES: Determination of germination and mortality rates, assessment of plant physiological parameters. Quantification of plant biomass, heavy metals in plants, total petroleum hydrocarbons (TPH) in soil, soil microbiological indicators. Calculation of phytoremediation parameters. REMARKABLE RESULTS : Alfalfa presented low tolerance to TPH contaminated soil at 8400 mg kg-1 soil, which was improved when TPH were present at lower concentration (3600 mg kg-1 soil). Alfalfa was able to take up metals to a limited extent (<100 mg kg-1 dry matter), while had a positive effect in promoting microbial number of alkane degraders and lipase activity in the rhizosphere. Moreover, the combined application of citric acid and Tween® 80 resulted in a greater improvement of these parameters. Bioaugmentation with P. aeruginosa had a promoting effect on alfalfa biomass (71% increase of plant total dry biomass). In addition, the highest TPH removal rates (68%, after 90 days of experiment) were obtained in soils vegetated with alfalfa and bioaugmented with P. aeruginosa.OVERALL CONCLUSION: Alfalfa could tolerate a heavy metal and petroleum hydrocarbon co-contaminated soil (subject to TPH levels), which is an essential characteristic for any plant species to be used in phytoremediation. Alfalfa could not be considered as an actively heavy metal removal species as it was not able to phytoextract significant amounts of heavy metals (still in the presence of soil amendments or bioaugmentation). Nevertheless, the enhancement of microbial number and activity in the rhizosphere encouraged the potential of this plant species to be successfully used in the remediation of petroleum hydrocarbons. These effects were additionally enhanced by the joint application of soil amendments. Finally, the combination of phytoremediation and bioaugmentation seems a promising approach to achieve the remediation of petroleum hydrocarbons, when present in multi-contaminated soils

Les bactéries jouent un rôle important dans le fonctionnement des sols et participent activement à l'altération des silicates. L'altération des silicates contrôle en partie la lixiviation d'éléments minéraux majeurs essentiels en solution (maintien de la fertilité des sols). Cependant, si les principaux processus d'altération des silicates sont bien connus en milieu aérobie (acidolyse et complexolyse), cette fonction d'altération bactérienne des silicates n'a jamais été utilisée comme indicateur biologique de la fertilité des sols. Le premier objectif de ce travail de thèse a donc été d'identifier les processus d'altération de 2 micas par des bactéries hétérotrophes en utilisant un modèle d'altération empirique basé sur l'activité des protons et ligands pour identifier et étudier les interactions entre les bactéries et les minéraux. Le traçage des processus d'altération par les isotopes stables du Mg a également été testé. Le second objectif a été de corréler la fonction d'altération de communautés bactériennes aux conditions naturelles rencontrées dans différents sols. Ce travail confirme que l'oxydation partielle du glucose en acides organiques est le mécanisme prédominant par lequel les bactéries amplifient la lixiviation d'éléments en condition aérobie lors de l'altération de la biotite et de la phlogopite, surtout pour des pH proches de la neutralité. Le modèle empirique utilisé a été adapté pour permettre de comparer les taux de libération initiaux du fer lors de l'altération abiotique et bactérienne de micas afin d'identifier les 2 processus majeurs impliqués. Cette approche a permis de mettre en évidence des phénotypes d'altération en fonction du métabolisme, la compétence des souches bactériennes utilisées et des conditions expérimentales. L'étude menée avec les isotopes stables du Mg comme traceurs d'altération n'a pas montré de fractionnements signant chaque processus. L'utilisation du modèle a ensuite permis de montrer que le potentiel d'altération des silicates par les communautés bactériennes dépend de leur origine et en particulier des teneurs en MO et en nutriments des horizons de sols échantillonnés. Deux stratégies d'altération des silicates par ces communautés ont été mises en évidence : (1) les communautés bactériennes isolées des horizons riches en nutriments libèrent peu d'acides organiques, mais très complexants (stratégie K), (2) les communautés isolées d'horizons pauvres en nutriments libèrent beaucoup d'acides organiques peu complexant (stratégie r). L'approche interdisciplinaire proposée dans ce travail permet d'identifier et de caractériser les processus d'altération de phyllosilicates par des bactéries et offre un outil d'identification fonctionnel prometteur pour évaluer la qualité des sols / The bacteria play an important role in soil functioning and are also involved to the weathering of silicate minerals. The silicate weathering controlled the leaching of essential major mineral elements in solution, essential to maintaining soil fertility. However, although the main weathering processes of silicates are well known in aerobic (the proton- and ligand-promoted dissolution), this function of bacterial weathering of silicate minerals has never been used as a biological indicator of soil fertility. The first aim of this work was therefore to identify the process of weathering in two phyllosilicates by heterotrophic bacteria, using an empirical model of silicates weathering based on the activity of protons and ligands to identify and study the interactions between bacteria and minerals. Tracing of weathering processes by isotopic approach using stable isotopes of Mg has also been tested. The second aim was to correlate the “silicate weathering” function of bacterial communities of various soils in field conditions. This study confirms that the partial oxidation of glucose to organic acids is the predominant mechanism by which bacteria accelerate the leaching of elements under aerobic conditions during the weathering of biotite and phlogopite especially at pH close to neutrality. The empirical model used has been adapted to compare the initial release rate of iron in bacterial and abiotic weathering of micas to identify the two major processes involved. This approach highlighted the identification of phenotypes according to the metabolism and the competence of the bacterial strains used. The study with stable isotopes of Mg as tracers of weathering showed no fractionation during the proton- and ligand-promoted dissolution. Using the model in the second part of this work showed that the silicate weathering potential by microbial communities depends on their origin and in particular the contents of OM and nutrients of soil horizons sampled. Two strategies of silicate weathering in these communities have been identified: (1) the bacterial communities isolated from nutrient-rich horizons released few organic acids, but very chelating (strategy K), (2) communities isolated from nutrient-poor horizons release many low chelating organic acids (strategy r). The interdisciplinary approach proposed in this work to identify and characterize the weathering of phyllosilicates by soil heterotrophic bacteria or communities in different environments. It provides a original and promising tool for identifying functional to evaluate the quality of natural soils

A matéria orgânica do solo (MOS) é composta de uma mistura complexa e heterogênea de compostos orgânicos, sendo as substâncias húmicas (SH) a fração mais recalcitrante da MOS. As SH têm grande influência sobre as propriedades químicas e biológicas do solo, contribuindo como fonte de energia para microrganismos e também contribuindo com a disponibilidade de nutrientes. Além disso, as SH podem contribuir de forma expressiva para o desenvolvimento e produção das plantas cultivadas. Neste sentido, o objetivo deste trabalho foi avaliar a atividade e diversidade da comunidade bacteriana do solo, a disponibilidade de nutrientes e a produtividade da cultura de trigo após aplicação de doses crescentes de SH. Dois experimentos foram montados e avaliados, sendo um ensaio de incubação com um solo arenoso e outro um experimento de casa de vegetação com plantas de trigo em dois solos tropicais distintos (textura arenosa e argilosa). Houve um estímulo à atividade microbiana em ambos os experimentos, sendo este estímulo transitório, o que provavelmente ocorreu devido a um efeito priming provocado pela adição de SH. No entanto não houve alteração na estrutura da comunidade bacteriana pela adição de SH, o que pode ser devido ao fato de ser um material recalcitrante e já presente no solo. Também houve aumento na disponibilidade de fósforo, potássio, cálcio e nitrogênio, bem como da CTC, tanto em solo arenoso quanto argiloso, expressando o efeito das SH na melhoria das propriedades químicas de solos tropicais. Além disso, um efeito significativo foi visto em parâmetros relacionados à produtividade do trigo. Houve aumento de massa seca de raízes e parte aérea, além de aumento no peso e número de grãos, o que pode se refletir em aumento considerável de produtividade. Esses resultados são importantes por mostrarem que mesmo a fração mais recalcitrante da MOS pode influenciar positivamente aspectos químicos e biológicos do solo, contribuindo com a melhoria do sistema de produção e também com maiores produtividades vegetais. / The soil organic matter (SOM) is composed of a complex and heterogeneous mixture of organic compounds, in which the humic substances (HS) are considered to be the most recalcitrant fraction. HS have great influence on chemical and biological soil properties, contributing as energy source for microorganisms and as nutrient reservoir for plants. Furthermore, HS can contribute significantly to the development and production of crop plants. Therefore, the objective of this study was to evaluate the activity and diversity of the soil bacterial community, nutrient availability and productivity of a wheat crop after application of increasing doses of HS. For this purpose, two experiments were performed and evaluated, one is an incubation essay with a sandy soil and the other a greenhouse experiment with wheat plants using two distinct tropical soils as substrates (sandy and clayey). Microbial activity was stimulated in both experiments, and this transient stimulus may have been due to a priming effect caused by the addition of HS. However, there was no change in the bacterial community structure which may be due to the fact that HS is a recalcitrant material and already present in the soil. Nevertheless, we found an increase in the availability of phosphorus, potassium, calcium and nitrogen, as well as in the CEC in both, sandy and clayey soils, showing that HS do improve chemical properties of tropical soils. Furthermore, we found a significant effect on wheat productivity related parameters. There was an increase of dry weight of roots and shoots, as well as increased weight and number of grains, which may be reflected in a significant increase in productivity. These results are important because they show that even the most recalcitrant SOM fraction can positively influence soil chemical and biological aspects, contributing to the improvement of the production system and also to higher plant productivity.

Resumo: O uso de bactéria como agente catalítico para a lixiviação de sulfetos minerais é largamente reconhecido hoje como uma metodologia interessante, sob o ponto de vista econômico e ambiental, para a recuperação de metais de minérios de baixo teor e minérios de sulfetos secundários. A principal bactéria envolvida neste processo é a Acidithiobacillus ferrooxidans, um microrganismo quimiolitotrófico e acidofílico que obtem energia através da oxidação do íon Fe2+, além das formas reduzidas de enxofre e sulfetos metálicos. Dentre os principais sulfetos metálicos encontrados nas reservas minerais de cobre, a calcopirita (CuFeS2) é a que mais se destaca por ser o mineral mais abundante e ao mesmo tempo mais refratário ao ataque químico e bacteriano. Dentro desse contexto há um grande interesse no desenvolvimento de alternativas para otimizar a solubilização desse sulfeto. Neste trabalho, foram investigados o efeito dos ácidos orgânicos e dos íons cloreto e na biolixiviação da calcopirita visando aumentar a solubilização de cobre desse sulfeto. Com relação ao estudo com os ácidos orgânicos (cítrico e oxálico) foi observado que a linhagem bacteriana A. ferrooxidans-LR foi inibida na presença do ácido oxálico em concentrações acima de 0,10 % m/v. Na presença de ácido cítrico não foi observado nenhuma inibição nas diversas concentrações utilizadas. Em função desses resultados o ácido cítrico foi o único a ser utilizado nos ensaios posteriores. O teste de solubilização das jarositas demonstrou que uma vez formada, ela não pode ser dissolvida pela adição de ácido cítrico. No entanto, este ácido mostrou-se eficiente para conter a formação destes precipitados. Os ensaios de biolixiviação na presença de ácido cítrico foram acompanhados por 60 dias através de medidas de pH, Eh, [Fe2+], [Fe3+] e [Cu]... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Acidithiobacillus ferrooxidans is a chemolithoautotrophic and acidophilic bacterium which obtain their energy through oxidation of the iron Fe+2 or sulfur reduced compounds including metal sulfides. This is the main species involved in the metals bioleaching process, an useful methodology to recovery metals from low-grade ores and secondary mineral sulfides. Chalcopyrite (CuFeS2) is one of the most abundant mineral of copper but at same time the most refractory, both to chemical and biological dissolution. So, it would be interesting to develop alternative technologies to improve copper solubilization from this sulfide. In the present study, it was investigated the effect of chlorine ions and organic acids in the chalcopyrite dissolution by bioleaching experiments in shake flask, following parameters such as pH, Eh, [Fe2+], [Fe3+] and [Cu]. Solid residues collected during and at end of assays were analyzed by X rays diffraction technique. The presence of Cl- ions (150 mmol L-1) and bacterium cells increased the degree of the chalcopyrite dissolution, comparing to abiotic controls and without Cl- ions. Two kinds of cell adaptation were also investigated regarding their capacity of copper extraction. Chlorine adapted cells showed better results than those adapted only to grow in chalcopyrite. Indeed, successive Cl- ions addition during experiment time course, at 10 e 20 mmol L-1, enhanced copper extraction in about 70% in comparison to that of 150 mmol L-1 in just one addition. The main new solid phase obtained during bioleaching experiments in inoculated flasks was covelllite, but jarosites were not produced in these conditions, which can be considered a promising result. The successive chlorine ion addition in bioleaching of chalcopyrite showed to be a potential procedure to improve copper extraction. Basically, the studies of organic acids (citric and oxalic)... (Complete abstract click electronic access below) / Orientador: Oswaldo Garcia Júnior / Coorientador: Denise Bevilaqua / Banca: Assis Vicente Bendetti / Banca: Ana Teresa Lombardi / Mestre

This master thesis deals with the investigation of selected chemical and sensory characteristics of ciders, which were made from four selected apple varieties. The theoretical part describes the chemical composition of apples, cider, the technology of production and production in the world. The next section describes the analytical methods used to determine chemical characteristics not only in ciders but also in other alcoholic beverages. The experimental part focuses on the determination of chemical characteristics such as the content of organic acids, carbohydrates, total phenolic content, alcohol antioxidant activity and elemental composition. The purpose of the work was to find out how different varieties differ in chemical composition. The produced ciders were subjected to sensory analysis to evaluate the selected cider sensory parameters, which were in the natural state and with the addition of carbon dioxide. The results show that ciders of different varieties differ in chemical composition. Malic acid was the most cider's abundant of the organic acids in the range of 2759 – 4411 mg·l-1. Another acid represented was lactic acid in the range of 166,2 – 288,1 mg·l-1. The glucose content of each cider was determined between 845,3 – 1159,8 mg·l-1and fructose 32,6 – 406,7 mg·l-1. Potassium 944,29 – 1073,98 mg·l-1 was the most represented of all elements. The total phenolic content was determined to be in the range of 164,2 – 214,1 mg of GAE·l-1and the antioxidant activity of 0,192 – 0,318 mg·l-1. These differences in chemical composition were also reflected in sensory evaluation. According to the overall assessment, the best cider was made from the Granny Smith variety, which contained the most organic acids and carbohydrates. It has been found that by adding carbon dioxide, sensory parameters such as colour, taste and smell are altered.

The aim of this master’s thesis is perform basic analyses of samples ketchups. The theoretical part describes the basic characteristics of tomato, tomatoes processing and production of puree and ketchup. Then there are described analytical methods which were used for analysing the selected parameters in ketchups. The experimental part deals with the determination of pH, total solids, organic acids, saccharides, macroelements and lycopene in ketchups. Citrate and acetate were analysed by IC. The amount of acetate in ketchups was about 5 times greater than the amount of citrate. Glucose, fructose and sucrose were analysed by HPLC. Glucose and fructose were determined in all samples but sucrose not. The ICP-OES method was used to determine four elements. Magnesium was the least represented element and sodium was the most represented element in the analysis. The amount of sodium was recalculated on the amount of salt. Lycopene was analysed by UV-VIS spectrometry. Its amount in ketchups is influenced by the variety of used tomatoes and plenty of other factors.