L'objectif principal de ce travail est d'évaluer si l'amendement calco-magnésien de deux bassins versants acidifiés du massif vosgien (un sur grès et un sur granite) engendre des changements de la morphologie des humus, de l'abondance et de la diversité de la mésofaune, de la biomasse fongique, du stockage de carbone dans les horizons organiques 5 et 7 ans après l'amendement. Par ailleurs, nous avons effectué une étude dans des conditions contrôlées de laboratoire en utilisant des microcosmes contenant les horizons organiques du sol provenant de bassins versants acidifiés sur grès et sur granite afin d'évaluer les effets à court terme de l'amendement. Les résultats indiquent que les effets de l'amendement sont beaucoup plus marqués sur le substrat le plus acide. À court terme, sur substrat gréseux, nous observons une diminution de l'abondance de la mésofaune puis une augmentation de celle-ci 5 ans après l'amendement avant de ne montrer plus aucun effet 7 ans après l'épandage. L'effet inverse ou aucun effet n'est par contre observé sur substrat granitique. Le contenu en Ca et Mg de l'horizon OL a augmenté avec l'amendement, mais cet effet n'est également significatif que sur grès. La biomasse fongique du sol n'a pas été affectée par le chaulage, mais est significativement plus élevée sur granite que sur grès. Le chaulage a augmenté l'épaisseur de l'horizon OH sur grès alors qu'il a diminué l'épaisseur de l'horizon OL sur granite, probablement en relation avec les modifications de l'activité biologique (mésofaune ou microorganismes). Enfin, sur substrat gréseux, le stock de carbone de l'humus a augmenté du fait d'un épaississement notable de l'horizon OH avec le chaulage. / The main objective of this work is to assess the consequences of calco-magnesium liming on two acidified forested catchments in Vosges Mountain (sandstone and granite) on humus morphology, abundance and diversity of mesofauna, fungal biomass and carbon storage in organic horizons 5 and 7 years after liming. Moreover, we performed a study to verify under laboratories conditions by using microcosms filled with soil from acidified catchments lying on sandstone and granite in order to study the short-term effect of calco-magnesium liming. During the two field campaigns, we determined calcium and magnesium contents of OL horizon, pH, humus morphology, mesofauna abundance and diversity, fungal biomass, soil carbon storage of organic layers OL, OF and OH.Results indicated that calco-magnesium liming affects studied parameters in different ways according to elapsed time after liming and the geological substrate (sandstone and granite), the more acidic catchment (sandstone) showing the most remarkable reaction. Results of immediate effects of liming showed a decrease of mesofauna abundance and then gradually increasing tendencies in field campaigns after 5 years while no effect after 7 years after liming. The opposite or no effects were observed on granite substrate. Ca and Mg contents in OL horizon increased by liming but this effect were only significant on sandstone substrate. Soil fungal biomass was not affected by liming but was significantly higher on granite substrate than sandstone. Liming increased the OH horizon thickness on sandstone while decreased the OL horizon on granite, under the influence of biological activity (mesofauna vs microorganisms).

Soil organic matter (SOM) is the terrestrial biosphere's largest pool of organic carbon (C) and is an integral part of C cycling globally. Soil organic matter composition typically can be traced directly back to the type of detrital inputs; however, the stabilization of SOM results as a combination of chemical recalcitrance, protection from microbial decomposition within soil structure, and organo-mineral interactions. A long-term manipulative field experiment, the Detrital Input and Removal Treatment (DIRT) Project, was established to examine effects of altering detrital inputs (above- vs. below-ground source, C and nitrogen (N) quantity, and chemical quality) on the stabilization and retention of SOM. Surface mineral soil was collected from two DIRT sites, Bousson (a deciduous site in western Pennsylvania) and H.J. Andrews (a coniferous site in the Oregon Cascade Mountains), to examine the influence of altering detrital inputs on decomposability and mean residence time of soil organic matter and different organic matter fractions. Soil organic matter was physically separated into light fraction (LF) and heavy fraction (HF) organic matter, by density fractionation in 1.6 g mL⁻¹ sodium polytungstate (SPT). Density fractionation in SPT resulted in the mobilization and loss of ~25% of total soil organic C and N during the physical separation and rinsing of fractions during recovery, which was also the most easily decomposed organic matter present in the bulk soil. At H.J. Andrews, this mobilized organic matter had a short mean residence time (MRT), indicating that it originated from fresh detrital inputs. In contrast, at Bousson, the organic matter mobilized had a long MRT, indicating that it originated from organic matter that had already been stabilized in the soil. Mean residence times of LF from Bousson varied widely, ~3 y from doubled litter and control plots and 78-185 y for litter removal plots, while MRT of HF was ~250 y and has not yet been affected by litter manipulations. Results from long term incubation of LF and HF material supported these estimates; respiration was greatest from LF of doubled litter and control plots and least from HF of litter removal plots. In contrast, MRT estimated for LF and HF organic matter from H.J. Andrews were similar to each other (~100 y) and were not affected by litter manipulation. These estimates were also supported by the incubation results; there was not a difference in cumulative respiration between detrital treatments or density fractions. The results from the coniferous site may be due to a legacy of historically large inputs of coarse woody debris on the LF and it may be decades before the signal of detrital manipulations can be measured. Alternatively, these highly andic soils may be accumulating C rapidly, yielding young HF ages and C that does not differ substantially in lability from coniferous litter-derived LF. The DIRT Project was intended to follow changes in soil organic matter over decades to centuries. As expected, manipulation of detrital inputs has influenced the lability and mean residence time of the light fraction before the heavy fraction organic matter; however, it will be on much more lengthy time scales that clear differences in organic matter stabilization in response to the alteration of detrital inputs will emerge. Soil CO₂ efflux is a compilation of CO₂ from many sources, including root respiration and the decomposition of different organic matter fractions, roots, and exudates. If the sources of CO₂ have different isotopic signatures, the isotope analysis of CO₂ efflux may reveal the dominant sources within the soil profile. In a short incubation experiment of density fractions from both sites, respired CO₂ reflected the isotopic signature of the organic matter fraction after 30 days, but was more enriched in ¹³C. Initially CO₂ was isotopically depleted in ¹³C relative to the organic matter fraction and the period of depletion related to the amount of easily degraded organic matter present at H.J. Andrews only. / Graduation date: 2006

A major argument for incorporating deciduous tree species in coniferous forest stands is their role in the amelioration and stabilisation of biogeochemical cycles. Current forest management strategies in central Europe aim to increase the area of mixed stands. In order to formulate statements about the ecological effects of mixtures, studies at the stand level are necessary. In a mixed stand of Norway spruce (Picea abies (L.) Karst.) and silver birch (Betula pendula Roth) in the Ore Mountains (Saxony, Germany), the effects of these two tree species on chemical and microbial parameters in the topsoil were studied at one site in the form of a case study. Samples were taken from the O layer and A horizon in areas of the stand influenced by either birch, spruce or a mixture of birch and spruce. The microbial biomass, basal respiration, metabolic quotient, pH-value and the C and N contents and stocks were analysed in the horizons Of, Oh and A. Significantly higher contents of microbial N were observed in the Of and Oh horizons in the birch and in the spruce-birch strata than in the stratum containing only spruce. The same was found with respect to pH-values in the Of horizon and basal respiration in the Oh horizon. Compared to the spruce stratum, in the birch and spruce-birch strata, significantly lower values were found for the contents of organic C and total N in the A horizon. The findings of the case study indicated that single birch trees have significant effects on the chemical and microbial topsoil properties in spruce-dominated stands. Therefore, the admixture of birch in spruce stands may distinctly affect nutrient cycling and may also be relevant for soil carbon sequestration. Further studies of these functional aspects are recommended.

No description available.

Conselho Nacional do Desenvolvimento Científico e Tecnológico (CNPq) / Estudos relatam que a matéria orgânica proveniente das células de cianobactérias é um importante precursor na formação de subprodutos da desinfecção (DBP), tais como trihalometanos totais (THM), o que é considerado indesejável, principalmente quando se adotam processos oxidativos avançados (POA) para o tratamento da água. Embora este processo induza a degradação dos compostos orgânicos, a mineralização completa destes pode não ser alcançada. Se o tratamento não for efetivo, a matéria orgânica é oxidada parcialmente, tendo como subproduto da oxidação o carbono orgânico assimilável (COA), podendo assim propiciar um aumento de precursores de trihalometanos. Este estudo teve por objetivo avaliar a formação de carbono orgânico assimilável ao partir do processo oxidativo UV/H2O2 de água contendo células de cianobactéria e a sua correlação com a formação de trihalometanos. O desenvolvimento experimental do estudo foi dividido em duas etapas principais, sendo: adaptação da metodologia padronizada para quantificação de COA, e ensaios foto-oxidativos em diferentes condições operacionais. Na primeira etapa, a metodologia padronizada com os organismos P-17 e NOX foi adaptada, substituindo-se a técnica de avaliação do crescimento microbiano usual (contagem por placas) pela técnica de citometria de fluxo. Na segunda etapa, foram realizados ensaios foto-oxidativos a partir da exposição de água contendo células de Microcystis aeruginosa ao processo oxidativo UV/H2O2 em diferentes dosagens de H2O2 (10, 25, 50, 75 e 100 mg L-1 ) a uma densidade celular de 250.000 cel mL-1 . Nesta etapa foram monitorados os parâmetros pH, residual de peróxido de hidrogênio, densidade de células de cianobactérias, carbono orgânico assimilável, carbono orgânico dissolvido (COD), e a formação de trihalometanos. A partir dos resultados obtidos, pode-se observar que a aplicação de processo UV/H2O2 no tratamento de águas com a presença de cianobactérias de fato contribui para a formação de COA, porém neste caso, essa formação não foi diretamente proporcional à formação de THM, como era esperado. Observou-se que enquanto a concentração de COA aumentou após a oxidação, o inverso ocorreu com a concentração de THM, o qual apresentou uma redução significativa após a oxidação. A concentração de COD obtida mostrou uma tendência similar a formação de THM, pois a concentração de ambos foi reduzida ao longo do processo oxidativo. Relacionando os dados de COD e COA pode-se observar que estes também apresentaram comportamento inverso. Enquanto a concentração de COD diminuiu, a de COA aumentou após a oxidação. Do ponto de vista da eficiência do processo UV/H2O2 na remoção de matéria orgânica proveniente de células de cianobactérias e (ou) precursores de DBP’s, a aplicação deste processo se mostrou uma alternativa factível no tratamento de águas contaminadas pela M. aeruginosa. / Studies have reported that organic matter from cyanobacteria cells is an important precursor in the formation of disinfection by-products (DBP), such as total trihalomethanes (THM), which is considered undesirable, especially when adopting advanced oxidative The treatment of water. Although this process induces the degradation of organic compounds, complete mineralization of these compounds may not be achieved. If the treatment is not effective, the organic matter is partially oxidized, with the assimilable organic carbon (AOC) as the by-product of oxidation, which may lead to an increase in trihalomethane precursors. This study aimed to evaluate the formation of organic carbon assimilable from the UV/H2O2 oxidative process of water containing cyanobacteria cells and its correlation with the formation of trihalomethanes. The experimental development of the study was divided into two main steps: adaptation of the standardized methodology for AOC quantification, and photo oxidative assays under different operating conditions. In the first step, the methodology standardized with the P-17 and NOX organisms was adapted, replacing the usual microbial growth evaluation technique (plate counting) using the flow cytometry technique. In the second step, photo-oxidative assays were performed from the exposure of water containing Microcystis aeruginosa cells to the UV/H2O2 oxidative process at different dosages of H2O2 (10, 25, 50, 75 and 100 mg L-1 ) at a density of 250.000 cell mL-1 . The pH, residual hydrogen peroxide, cell density of cyanobacteria, assimilable organic carbon, dissolved organic carbon (DOC), and the formation of trihalomethanes were monitored. From the obtained results, it can be observed that the application of UV/H2O2 process in the treatment of water contaminated by cyanobacteria does indeed contribute to the formation of AOC, however in this case, this formation was not directly proportional to the formation of THM, as Was expected. It was observed that while the concentration of AOC increased after oxidation, the inverse occurred with the concentration of THM, which showed a significant reduction after the oxidation. The DOC concentration obtained showed a tendency similar to THM formation, since the concentration of both was reduced throughout the oxidative process. Relating the data of DOC and AOC can be observed that these also presented an inverse behavior. While DOC concentration decreased, AOC increased after oxidation. From the point of view of the efficiency of the UV/H2O2 process in the removal of organic matter from cyanobacterial cells and (or) DBP precursors, the application of this process has proved to be a viable alternative in the treatment of water contaminated by M. aeruginosa.

Conselho Nacional do Desenvolvimento Científico e Tecnológico (CNPq) / Estudos relatam que a matéria orgânica proveniente das células de cianobactérias é um importante precursor na formação de subprodutos da desinfecção (DBP), tais como trihalometanos totais (THM), o que é considerado indesejável, principalmente quando se adotam processos oxidativos avançados (POA) para o tratamento da água. Embora este processo induza a degradação dos compostos orgânicos, a mineralização completa destes pode não ser alcançada. Se o tratamento não for efetivo, a matéria orgânica é oxidada parcialmente, tendo como subproduto da oxidação o carbono orgânico assimilável (COA), podendo assim propiciar um aumento de precursores de trihalometanos. Este estudo teve por objetivo avaliar a formação de carbono orgânico assimilável ao partir do processo oxidativo UV/H2O2 de água contendo células de cianobactéria e a sua correlação com a formação de trihalometanos. O desenvolvimento experimental do estudo foi dividido em duas etapas principais, sendo: adaptação da metodologia padronizada para quantificação de COA, e ensaios foto-oxidativos em diferentes condições operacionais. Na primeira etapa, a metodologia padronizada com os organismos P-17 e NOX foi adaptada, substituindo-se a técnica de avaliação do crescimento microbiano usual (contagem por placas) pela técnica de citometria de fluxo. Na segunda etapa, foram realizados ensaios foto-oxidativos a partir da exposição de água contendo células de Microcystis aeruginosa ao processo oxidativo UV/H2O2 em diferentes dosagens de H2O2 (10, 25, 50, 75 e 100 mg L-1 ) a uma densidade celular de 250.000 cel mL-1 . Nesta etapa foram monitorados os parâmetros pH, residual de peróxido de hidrogênio, densidade de células de cianobactérias, carbono orgânico assimilável, carbono orgânico dissolvido (COD), e a formação de trihalometanos. A partir dos resultados obtidos, pode-se observar que a aplicação de processo UV/H2O2 no tratamento de águas com a presença de cianobactérias de fato contribui para a formação de COA, porém neste caso, essa formação não foi diretamente proporcional à formação de THM, como era esperado. Observou-se que enquanto a concentração de COA aumentou após a oxidação, o inverso ocorreu com a concentração de THM, o qual apresentou uma redução significativa após a oxidação. A concentração de COD obtida mostrou uma tendência similar a formação de THM, pois a concentração de ambos foi reduzida ao longo do processo oxidativo. Relacionando os dados de COD e COA pode-se observar que estes também apresentaram comportamento inverso. Enquanto a concentração de COD diminuiu, a de COA aumentou após a oxidação. Do ponto de vista da eficiência do processo UV/H2O2 na remoção de matéria orgânica proveniente de células de cianobactérias e (ou) precursores de DBP’s, a aplicação deste processo se mostrou uma alternativa factível no tratamento de águas contaminadas pela M. aeruginosa. / Studies have reported that organic matter from cyanobacteria cells is an important precursor in the formation of disinfection by-products (DBP), such as total trihalomethanes (THM), which is considered undesirable, especially when adopting advanced oxidative The treatment of water. Although this process induces the degradation of organic compounds, complete mineralization of these compounds may not be achieved. If the treatment is not effective, the organic matter is partially oxidized, with the assimilable organic carbon (AOC) as the by-product of oxidation, which may lead to an increase in trihalomethane precursors. This study aimed to evaluate the formation of organic carbon assimilable from the UV/H2O2 oxidative process of water containing cyanobacteria cells and its correlation with the formation of trihalomethanes. The experimental development of the study was divided into two main steps: adaptation of the standardized methodology for AOC quantification, and photo oxidative assays under different operating conditions. In the first step, the methodology standardized with the P-17 and NOX organisms was adapted, replacing the usual microbial growth evaluation technique (plate counting) using the flow cytometry technique. In the second step, photo-oxidative assays were performed from the exposure of water containing Microcystis aeruginosa cells to the UV/H2O2 oxidative process at different dosages of H2O2 (10, 25, 50, 75 and 100 mg L-1 ) at a density of 250.000 cell mL-1 . The pH, residual hydrogen peroxide, cell density of cyanobacteria, assimilable organic carbon, dissolved organic carbon (DOC), and the formation of trihalomethanes were monitored. From the obtained results, it can be observed that the application of UV/H2O2 process in the treatment of water contaminated by cyanobacteria does indeed contribute to the formation of AOC, however in this case, this formation was not directly proportional to the formation of THM, as Was expected. It was observed that while the concentration of AOC increased after oxidation, the inverse occurred with the concentration of THM, which showed a significant reduction after the oxidation. The DOC concentration obtained showed a tendency similar to THM formation, since the concentration of both was reduced throughout the oxidative process. Relating the data of DOC and AOC can be observed that these also presented an inverse behavior. While DOC concentration decreased, AOC increased after oxidation. From the point of view of the efficiency of the UV/H2O2 process in the removal of organic matter from cyanobacterial cells and (or) DBP precursors, the application of this process has proved to be a viable alternative in the treatment of water contaminated by M. aeruginosa.

Die bei der Biogasproduktion anfallenden Gärreste werden als organische Dünger im Pflanzenbau eingesetzt. Infolge des Vergärungsprozesses unterscheiden sich Gärreste von herkömmlichen organischen Düngern. Daraus könnten sich spezifische positive oder negative Wirkungen auf Bodenfruchtbarkeit und Pflanzen ergeben, die Gegenstand dieser Arbeit sind. In einem sechsjährigen Feldversuch (Energiepflanzenfruchtfolge, sandiger Boden) wur- den die Düngeeffekte von fünf verschiedenen Gärresten mit denen von Rindergülle, Stallmist und mineralischem Dünger (KAS) verglichen. Zur umfassenden Charakterisie- rung der Bodenfruchtbarkeit erfolgten Untersuchungen aus den Bereichen Bodenchemie, -physik, -mikrobiologie und Pflanzenbau, wobei die Humusdynamik einen Schwerpunkt bildete. Die Mengenkalkulation der Düngung basierte auf der gleichen Gabe organi- schem C mit einem N-Ausgleich durch KAS. Es ergaben sich für Gärreste gegenüber KAS überwiegend positive Effekte auf Hu- musgehalt, Aggregatstabilität und bakterielle Aktivität und Diversität. Diese Effekte waren denen von Rindergülle und Stallmist ähnlich. Möglicherweise besteht aber durch Gärrestdüngung ein erhöhtes Risiko von P- und K-Überschüssen sowie N-Verlusten. Eine erhöhte Benetzungshemmung wurde nicht gefunden. Die mikrobielle Gemeinschaft des Bodens zeigte eine spezifische Beeinflussung durch die Gärreste in der funktionellen, jedoch nicht in der genetischen Struktur. Die N-Verfügbarkeit war deutlich geringer als die von KAS, wodurch sich für Grünroggen Mindererträge ergaben. Für Silomais und Sorghum fand sich bei kombinierter Anwendung mit KAS ein zu KAS ähnliches Ertragsniveau. Gärreste haben analog zu herkömmlichen organischen Düngern bei effizientem Einsatz das Potential zu KAS vergleichbare Erträge zu erzielen und gleichzeitig die Bodenfrucht- barkeit zu fördern. Diese Schlussfolgerung ist im Kontext der spezifischen Standort- und Versuchsbedingungen zu sehen und sollte durch eine längere Versuchszeit abgesichert werden. / Digestates arising during biogas production are used as organic fertilizers in agriculture. Due to the fermentation process, digestates have different properties from traditional organic fertilizers. This may result in specific positive or negative effects on soil fertility and plants, which are subject of this work. In a six year field experiment (energy crop rotation, sandy soil) fertilizer effects of five different digestates were compared with cattle slurry, farm yard manure and mineral fertilizer (KAS). For a comprehensive characterization of soil fertility effects, methods from the fields of soil chemistry, physics, microbiology and plant science were applied. One special focus of these investigations was humus dynamics. Manure doses were based on the same dose of organic carbon, resulting different N-doses were compensated by KAS. Compared with KAS, digestates showed predominantly positive effects on humus con- tent, soil aggregate stability and bacterial activity and diversity. These effects of di- gestates were similar to those of cattle slurry and farm yard manure. There may be an increased risk of P and K oversupply and N losses as a result of digestate fertilization. An increased soil water repellency was not found. The soil bacterial community was specifically influenced by digestates regarding its functional, but not regarding its genetic structure. Saprotrophic fungy were reduced by some digestates in comparison to KAS. N availability was considerably lower than of KAS, resulting in yield depressions of forage rye. For silage maize and sorghum, digestates combined with KAS equaled the yield level of KAS. If efficiently applied, digestates have like other organic fertilizers the potential to produce equal yields as KAS whilst enhancing soil fertility. This conclusion is restricted to the specific conditions of experimental site and design and must be verified during a longer experimental period.

Resumo: Substâncias Húmicas (SH), extraídas de turfa sob diferentes condições foram caracterizadas com o objetivo de se desenvolver nova metodologia de extração com elevado rendimento, baixo teor de cinzas e sem grandes alterações estruturais. Parâmetros como: tempo, temperatura, atmosfera de extração, razão solo/extrator, granulometria do solo, extrator e sua concentração foram avaliados e mostraram ter grande influência no processo. Pelos estudos feitos e resultados obtidos pode-se concluir para a amostra estudada que: 1 - a extração alcalina das substâncias húmicas utilizando-se hidróxido de potássio aumenta o rendimento e diminui o teor de contaminantes inorgânicos co-extraídos em relação ao procedimento utilizando hidróxido de sódio; 2 - a concentração do extrator influencia muito no rendimento, teor de cinzas, razão E4/E6, razão AH/AF e composição elementar das substâncias húmicas extraídas; 3 - 4 horas de extração são suficientes para extrair praticamente toda matéria orgânica presente na amostra; 4 - a razão solo/extrator não exerce influência no teor de matéria orgânica extraída, entretanto, a diminuição dessa razão eleva o teor de contaminantes inorgânicos no extrato húmico; 5 - espectros na região do infravermelho e visível mostraram que o aumento da temperatura de extração causa mudanças estruturais nos ácidos húmico e fúlvico...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Humic Substances (HS), extracted from the peat under different conditions were characterised with the aim of developing a methodology of extraction with high yields, low contents of ashes and without big structural alterations. Parameters such as: time, temperature, extraction atmosphere, soil/extractor ratios, soil granulemetry, extractor and its concentration were evaluated and showed to have great influence on the process. By the studies done and results obtained we can conclude to the studied sample that: 1. the alkaline extraction from the humic substances using potassium hydroxide increase the yields and reduce the contents of inorganic contaminator co-extracted in relation to the procedure that uses sodium hydroxide; 2. the concentration of the extractor influences very much on the yields, contents of ashes, E4/E6 ratios, AH/AF ratios and elementary composition of the extracted humic substances; 3. four hours of extraction are enough to extract almost all the organic material present in the sample; 4. the soil/extractor ratios does not exert any influence on the contents of the extracted organic material, however, the decrease of this ratio increases the contents of inorganic contaminator in the humic extract; 5. spectres in the region of the infrared and visible showed that the increase of temperature of extraction provokes structural changes in the humic and fulvic acids. It was also verified that the reduction of the contents of humic acid and elevation of the fulvic acid extracted with the increase of temperature; 6. the nitrogen atmosphere minimises the oxidation of the humic and fulvic acids during the extraction. The increase in time of extraction of the humic substances in the absence of nitrogen favours the oxidative processes; ...(Complete abstract, click electronic access below) / Orientador: Julio Cesar Rocha / Coorientador: Maysa Furlan / Banca: Clóvis Augusto Ribeiro / Banca: Antonio Salvio Mangrich / Mestre

Made available in DSpace on 2015-04-22T22:01:57Z (GMT). No. of bitstreams: 1 Wamber Boni de Souza.pdf: 2659314 bytes, checksum: 7f9a2f165e36496d3cc87db36897ea3e (MD5) Previous issue date: 2013-06-03 / Fundação de Amparo à Pesquisa do Estado do Amazonas / This work describes the mercury and a summary on toxicity of organomercury, as well as environmental importance of the HS, addressing structural aspects of the interaction between carboxylic groups from humic and fulvic acids and Hg, in two reviews. A third review is presented the Density Functional Theory (DFT) applied to theoretical study of mercury and its compounds. Environmental chemistry of Hg is extensively revised, especially the reduction process Hg2+  Hg+  Hg0. The Hg can also be found in forms organomercury, which the methylmercury (methyl-Hg, CH3Hg+) and dimethylmercury (dimethyl-Hg, CH3(Hg)2) are the most important. Structurally, the difference between the two forms of Hg is the number of methyl groups. Important tool in the consolidation of experimental data, theoretical calculations have proven that they are capable of complementing experimental results. The DFT B3LYP functional with LANL2DZ basis set are performed for the neutral structures dimethylmercury (Dimetil-Hg), methylmercury (MetHgCl), methylmercury bromide (MetHgBr), methylmercury iodide (MetHgI) and charged methylmercury (Met-Hg), methylmercury oxide ion (MetHgO-), methylmercury sulfide ion (METHgS-), methylmercury selenide ion (MetHgSe-). Additionally, the interaction of the Model of Humic Substance Molecules (MHSM) (Benzoic acid (AB), Phthalic acid (AFT), Salicylic acid (AS) e 2,4-dihydroxybenzoic acid (2,4-ADHBC) and carboxylic groups from fulvic acid (AFRS) structure proposed for the Suwannee River with Hg2+ has been investigated theoretically by using DFT method with high level B3LYP/ LANL2DZ model in order to contribute to the understanding of the behavior of Hg in nature. Findings show that the structure of methyl-Hg is more stable and less reactive than dimethyl-Hg. The bond lengths C-Hg on Met-Hg-X (X = Cl-, Br- and I-) increase with increasing volume. In the case of Met-Hg-X (X = O2-, S2- and Se2-), the bond length C-Hg remains virtually unchanged. The charge distribution analysis has revealed that the Hg oxidation tendency to reduce or anion depending on what is on. The trend of reduction/oxidation is accompanied by a greater stabilization energy (NBO) and ΔEL. The HUMO-LUMO orbital shows the structures Met-Hg-X (X = Cl-, Br- and I-) that has a larger Δε Met-Hg-X (X = O2-, S2- and Se2-). Finally, the use of B3LYP/LANL2DZ shows errors in bond length in relation to the experimental data varying between 4.74 and 6.43%. The results showed that the interaction between the carboxylic acid and Hg2+ ions indicate the occurrence of a reduction process rather than complexation in the MMSH. The interaction AB Hg ions formed with the carboxylic AB proved to be the most stable among all the MMSH-Hg. The highest values of stabilization energy of second order were observed by the molecules AB Hg e AFT Hg. Findings showed that the complexation and reduction depends on the location of the carboxyl groups in the structure of fulvic acid in the AFRS. Furthermore, the binding energy, geometry and energy gap is altered by interaction with the carboxylic groups of AFRS with Hg2+. / Esta tese descreve o mercúrio e um resumo sobre a toxicidade dos compostos organomercuriais, bem como a importância ambiental da SH, abordando aspectos estruturais da interação entre grupos carboxílicos dos ácidos húmicos e fúlvicos e Hg, em duas revisões. A terceira revisão é apresentada a Teoria do Funcional da Densidade (DFT) aplicada ao estudo teórico de mercúrio e seus compostos. A química ambiental do Hg é revista extensivamente, especialmente o processo de redução do Hg2+  Hg+  Hg0. O Hg pode ser encontrado também em formas organomercurais, das quais o metilmercúrio (metil-Hg, CH3Hg+) e dimetil-Hg (dimetil-Hg CH3(Hg)2) são as mais importantes. Estruturalmente a diferença entre as duas formas de Hg é a quantidade de grupos metilas. Ferramenta importante na consolidação de dados experimentais, os cálculos teóricos já comprovaram que são capazes de complementar resultados experimentais. A DFT e o funcional B3LYP com o conjunto de base LANL2DZ foram usados para a otimizações de geometria para as estruturas neutras dimetilmercúrio (Dimetil-Hg), cloreto de metilmercúrio (MetHgCl), brometo de metilmercúrio (MetHgBr), Iodeto de metilmercúrio (MetHgI) e carregadas metilmercúrio (Met-Hg), íon óxido de metilmercúrio(MetHgO-), íon sulfeto de metilmercúrio (METHgS-) e íon seleneto de metilmercúrio (MetHgSe-). Além disso, a interação dos grupos carboxílicos de moléculas modelos de substâncias húmicas (MMSH), (Ácido benzoico (AB), Ácido ftálico (AFT), ácido salicílico (AS) e ácido 2,4-diidroxibenzocarboxílico) e de ácido fúlvico (AFRS) de estrutura proposta do rio Suwannee com Hg2+ foi investigado teoricamente por DFT no nível de cálculos B3LYP/LANL2DZ, a fim de contribuir para o entendimento do comportamento do mercúrio na natureza. Os resultados mostram que a estrutura do metil-Hg é mais reativa e menos estável que a estrutura do dimetil-Hg. Os comprimentos de ligação C Hg no Met-Hg-X (X = Cl-, Br- e I-) aumentam com o aumento do volume. No caso do Met-Hg-X- (X = O2-, S2- e Se2-) o comprimento de ligação C Hg permanece praticamente inalterado. A análise de distribuição de carga revelou que o Hg apresenta tendência para redução ou oxidação dependendo do ânion que está ligado. A tendência de redução/oxidação é acompanhada por uma maior energia de estabilização (NBO) e ΔEL. Os orbitais HOMO-LUMO mostram que as estruturas Met-Hg-X (X = Cl-, Br- e I-) possuem maior Δε que Met-Hg-X- (X = O2-, S2- e Se2- ). Finalmente o uso do B3LYP/LANL2DZ apresentou erros nos comprimento de ligação em relação aos dados experimentais variando entre 4,74 e 6,43%. Para as MMSH os resultados mostraram de modo geral, que a interação entre os íons carboxílicos e Hg2+ indicam a ocorrência de um processo de redução ao invés de complexação. Entre todas as MMSH-Hg, a interação AB Hg formada com os íons carboxílicos da AB mostrou ser a mais estável. As moléculas AB Hg e AFT Hg possuem os maiores valores de energia de estabilização de segunda ordem. Especificamente para os AFRS, os resultados indicam que a complexação e redução dependem da localização dos grupos carboxílicos na estrutura de ácido fúlvico. Além disso, a energia de ligação, a geometria

Made available in DSpace on 2017-07-10T19:24:38Z (GMT). No. of bitstreams: 1 Morgana Suszek.pdf: 1631457 bytes, checksum: e053e20fe847bb2e96307ad30b523a38 (MD5) Previous issue date: 2005-11-11 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Green solid residues coming from urban pruner and rests of agricultural products and also swineculture effluents have been showing as one of the main problems in the urban and rural areas, because their insuitable discards, being differents enviromment impacts. A alternative in order to treatment of these residues and effluents is the aerobic composting followed by vermicomposting process. In this study, was of these evaluated the integration of the composting and vermicomposting in the biostabilization of the urban green solid residues using swine wastewater and commercial activator, furthermore being checked the quality of the earthworm humus obtained. The vermicomposts produced showed similarities in the values of the C/N ratio, nitrogen and potass, in relation to the earthworm humus made with cattle manure, indicating the possibility of the green residues use in consortium with swine wastewater in the organic fertilizer production. Metals zinc and copper in the vermicomposts were detected, however, in concentrations which don´t infer risk of the human health, plants and soil contamination. The vermicomposts from organic composts showed, in average, lower value of that metals in relation to cattle manure vermicomposts. / Resíduos sólidos verdes provenientes de podas urbanas e de sobras de produtos hortifrutigranjeiros, assim como efluentes das atividades de suinocultura, apresentam-se como um dos principais problemas nas áreas urbanas e rurais, pois seus descartes de forma inadequada, provocam diversos impactos ambientais. Uma alternativa para o tratamento desses resíduos e efluentes é a compostagem aeróbia seguida pelo processo de vermicompostagem. Neste estudo, avaliou-se a integração da compostagem e vermicompostagem na bioestabilização de resíduos sólidos verdes urbanos, inoculados com água residuária da suinocultura e ativador comercial, ainda aferindo-se a qualidade do húmus de minhoca obtido. Os vermicompostos produzidos apresentaram semelhanças nos valores da relação C/N, nitrogênio e potássio, em relação ao húmus de minhoca feito com esterco bovino, indicando a possibilidade do uso dos resíduos verdes em consórcio com água residuária da suinocultura na produção de adubos orgânicos. Foram detectados os metais zinco e cobre nos vermicompostos, entretanto, em concentrações que não inferem riscos de contaminação ao solo, às plantas ou à saúde humana. Os vermicompostos de compostos orgânicos apresentaram, em média, valores mais baixos desses metais em relação ao vermicomposto de esterco bovino.