A avaliação da ocorrência de interações hidrofóbicas em substâncias húmicas toma-se importante pois este tipo de interação pode afetar a dinâmica e a reatividade de contaminantes apoIares no ambiente e influenciar no controle biogeoquímico do carbono no solo, podendo contribuir para a mitigação do efeito estufa. Entretanto, devido à heterogeneidade química das substâncias húmicas associada à baixa energia envolvida neste tipo de interação, evidências ou detecções experimentais são difíceis. Neste trabalho avaliou-se a ocorrência de interações hidrofóbicas em substâncias húmicas e também em alguns componentes do solo utilizando a metodologia de marcador de spin, detectável por ressonância paramagnética eletrônica, e a supressão de fluorescência. A utilização de diferentes marcadores de spin (TEMPO, 5-SASL, 16-SASL e 5-MSSL) possibilitou avaliar que a interação estabelecida com o ácido húmico é predominantemente hidrofóbica. A forte imobilização do marcado r 5SASL no ácido húmico foi confirmada pela diminuição dos valores da taxa de difusão rotacional obtida por simulação espectral (109 s-1 em água e 106 s-1 em presença do ácido húmico). Da análise do comportamento espectral do marcador de spin, observou-se que a conformação estrutural do ácido húmico depende, além do pH, da concentração iônica. Em pH 7,5, foi observado que a utilização de concentrações iônicas acima de 0,1 moI L-1 de c1oreto de sódio favoreceu a formação de sítios hidrofóbicos menos expostos ao meio aquoso (internos). O tempo de hidratação e a concentração de ácido húmico também influenciaram na formação destes sítios. Os experimentos com variação de concentração de ácido húmico e de marcador de spin sugeriram que a estruturação de sítios hidrofóbicos internos, observados principalmente abaixo de pH 5, seja devida à agregação de várias estruturas húmicas menores. Embora tenha sido observada a existência de sítios hidrofóbicos no ácido fúlvico, este apresentou maior dificuldade de agregação em comparação ao ácido húmico, o que foi atribuído ao seu caráter mais hidrofílico. Dos experimentos de supressão de fluorescência, observou-se que a interação do pireno foi influenciada pelas características químicas dos ácidos húmicos extraídos de diferentes solos e sistemas de manejo. Os dados mostraram que quanto maior a aromaticidade do ácido húmico maior foi a interação, sugerindo que as interações estabelecidas ocorrem predominantemente por meio de forças de van der Waals. Não se obteve correlações significativas entre a porcentagem estimada de moléculas de marcadores de spin imobilizadas nos sítios hidrofóbicos internos com as características químicas dos ácidos húmicos. Este comportamento sugeriu que estes sítios podem estar mais associados à conformação estrutural do que à composição química dos ácidos húmicos. Também foi analisado o comportamento espectral do marcador de spin na presença de alguns componentes do solo (fração argila, solo tratado com ácido fluorídrico e ácido húmico). Pelos resultados não se observou imobilização do marcador de spin na fração argila (caulinita), diferentemente do que foi observado para o solo tratado com ácido fluorídrico e ácido húmico. As diferenças na imobilização dos marcadores de spin foram atribuídas aos diferentes teores de carbono de cada amostra. / Hydrophobic interactions can play an important role on the dynamics and reactivity of the apoIar organic compounds in the environrnent as well as the organic carbon dynamic in the global system, and eventually contribute to mitigation of greenhouse effect. However, due to the chemical heterogeneity of humic substances and the low energy involved in the hydrophobic interactions experimental evidences are very difficult to be obtained. ln this work, hydrophobic interactions in the humic substances and some soil components were evaluated through spin labeling, detected by electronic paramagnetic resonance, and fluorescence quenching. Using different spin labels (TEMPO, 5-SASL, 16-SASL and 5-MSSL), it was possible to observe that the interactions established with humic acids are mainly hydrophobic. The decrease of the values of the rotational diffusion rates, obtained from spectral simulation, from 109 s-1 Iin water to 106 s-1 in the presence of humic acid indicated that the spin label was strongly immobilized in the humic acid. The results from the analysis of spectral anisotropy of the spin label showed that conformational aspects of the humic acid are dependent on pH value and ionic strength. For pH around 7.5 and using ionic strength above 0.1 moI L-1 of sodium chloride was noticed an increase in the formation of inner hydrophobic sites. It was noticed that the formation of inner hydrophobic sites also was influenced by hydration time and humic acid concentration. Data obtained using different humic acids and spin label concentration suggested that the inner hydrophobic sites formation (mainly at pH below 5) is due to the aggregation of small humic structures. The existence of inner hydrophobic sites was noticed in the fulvic acid. However, the fulvic acid presented more difficulty to form aggregates, in comparison with humic acid, due to its major hydrophilic characteristic. From data obtained by fluorescence quenching it was observed that the interaction of pyrene was influenced by chemical composition of humic acid samples extracted from different soils and tillage systems. An increase of interactionin samples with higher aromaticity degree was shown, which indicates that the van der Waals forces are prevailing. No correlation between the estimated percentages of spin label molecules immobilized in the inner hydrophobic sites and the chemical characteristics of humic acid samples was obtained. This behavior suggested that the hydrophobic sites in the humic acid are mainly related to structural conformation instead of chemical composition. The mobility trend of spin label in the presence of soil components (clay fraction, fluoridric acid treated soil and humic acid) was also analyzed. No spin label immobilization was noticed in the clay fraction (kaolinite). On the other hand strongly immobilized spin label in the fluoridric acid treated soil and humic acid were observed. The differences in the immobilization were attributed to the carbon content.

The aim of this diploma thesis is to study to the influence of compost addition to soil humic substances extracted from blackland luvicsol. Humic substances extracted from soil and from compost were characterized by titration with potentiometrical and conductival indication, UV-VIS, FT-IR and 3D EEM fluorescential spectroscopy. Compost in amount of 124, 239 and 478 t/ha was applicated and manured into dept of 150 mm at blackland luvicsol. The main aim of thesis was the appraisal of compost influence into fluorescent attributes of soil HS and localization of fluorescent peaks at excitation emission spectrums. Next part of diploma thesis was focused on the study of spectroscopic attributes of soil HS and compost by UV-VIS and infrared spectroscopy with Fourier transformation. Humic substances were characterized by humifical index E4/E6 and transmissional vibratile spectrums. The last aim of diploma thesis were the characterization of soil HS extracts and compost by acidimetral titration. For each sample was calculated value of H+ ionts amount of substance from measured titrational curves.

This diploma thesis deals with the study of non-energy use of lignite. The main objective was to find an optimal recipe for the preparation of liquid and semi-solid (paste) hydrocolloids from the South Moravian lignite using the planetary mill and select the suitable dispersion medium with emphasis on possible use in agriculture. The used solutions were 10, 20 a 40 % w/w solutions of urea; 5, 10 a 15 % w/w solutions of citric acid; 1, 5 a 10 % w/w solutions of potassium chloride and deionized water. The best weight ratio for the preparation of lignite hydrocolloids is 1 part of lignite and 2 parts of the solution. The next part of this work is the isolation of humic acid from lignite hydrocolloids. The weight of isolated humic acids and amount of ash were compared to the used lignite hydrocolloids. Rheological behavior, particle size distribution, stability and thermal stablity of prepared lignite hydrocolloids were investigated. Correlation microscopy was used for determining elemental composition of selected location in the sample of lignite hydrocolloid.

This thesis deals with the study of the biological activity of humic substances. Based on the literature review preparation procedures were optimized in order to develop new hydrogel forms containing humic substances and biopolymers with high swelling capacity. Besides methodology for the rapid assessment of the biological activity obtained in laboratory conditions were designed and tested. The experimental part focused on characterization of hydrogel samples by means of routine physico-chemical methods, the main attention was paid to sorption of water and release of humic substances into solution. Then the prepared hydrogel materials were tested focusing on the growth effects on the maize. The absorption of mineral nutrients by the roots of plants were studied as well. The motivation of this work comes from the potential of agricultural and environmental applications of such hydrogel materials resulting in a renewal of previously exhausted organic content of soils and consequent interruption of substantial soil degradation.

Tato dizertační práce studuje charakter hydratační vody v systému voda/huminová látka. Úkolem je určit jak kvantitativní, tak i kvalitativní aspekty hydratace huminových látek (HS) v pevné i kapalné fázi a prozkoumat rozdíly ve vlastnostech vody obklopující huminovou látku s použitím vysokorozlišovací ultrazvukové spektroskopie (HRUS) a metod termické analýzy, jako je diferenční kompenzační kalorimetrie (DSC) a termogravimetrie (TGA). Hlavním cílem této práce je přispět k objasnění problému hydratace huminových látek pocházejících z různých zdrojů a majících proto odlišné vlastnosti a složení, a to s využitím postupů a technik, které se již dříve osvědčily při stanovení hydratační vody v hydrofilních polymerech. Tato práce zkoumá účinek vody na strukturu huminových látek, způsob, jakým voda smáčí jejich povrch a jak jimi proniká, způsobuje změny v konformaci HS, jejich retenční kapacitu a také vliv původu jednotlivých huminových látek na jejich hydratační vlastnosti s ohledem na kineticku těchto procesů. Dále studuje vliv stupně humifikace na hydratační procesy huminových látek, stejně jako reverzibilitu těchto procesů. Výsledky této práce objasňují paralelu s vlastnostmi hydrogelů a podobnosti i odlišnosti mezi biopolymery a huminovými látkami.

This thesis is focused on the study of the biological activity of superabsorbent polymers for environmental and agricultural applications. Generally these hydrogels perform many functions in the soil, which is increasingly stressed by treatment with synthetic fertilizers and thus loses their natural properties, such as the uptake of moisture. Addressing these issues is now in superabsorbent polymers that can absorb and also retain a lot of water around the root system as long as possible. They can perform the function of carriers gradual release fertilizer. Based on the literature review was designed and conducted the study of biological activity in the soil model on corn sown. SAPs were prepared in the framework of contract research Faculty of Chemistry of the Technical University in Brno with the company Amagro Ltd. The content of the experiment, the superabsorbent polymer, observing effects on the growth of dent corn. He was also studied root system for absorption of nutrients. Further changes were observed rheological properties of prepared superabsorbent polymer, superabsorbent polymers since they provide a source of nutrients and help to retain moisture in the soil, it is necessary to know their viskoelstick properties even at temperatures below freezing. This work is based primarily on the use of great motivation superabsorbent polymers in agriculture and also in environmental protection.

The aim of this study is the organomineral gel contained in soil, mainly the characterization using electron microscopy and available analytical methods like IR-spectrometry, thermal analysis, X-ray crystallography and emission spectrometry. The knowledge from this study may help to define function and significance of this gels to soils and nature. The theoretical part of this thesis deals with soil, humic substances and minerals occurring in soils. The experimental part solves especially the structure and further characterization of organomineral gels.

Orientador: Mara Cristina Pessoa da Cruz / Coorientador: Manoel Evaristo Ferreira / Banca: Wanderley José de Melo / Banca: José Carlos Barbosa / Banca: José Ricardo Mantovani / Banca: Renato Yagi / Resumo: A matéria orgânica do solo é fonte primária de nutrientes às plantas e é considerada um dos principais indicadores de sustentabilidade e qualidade do solo, de modo que é importante o conhecimento do teor de C orgânico total, das suas frações e das alterações que ocorrem quando há mudança no manejo. Com base nisso, foi objetivo do presente trabalho avaliar os efeitos da adubação com esterco bovino nos teores de carbono orgânico total, nitrogênio total e capacidade de troca de cátions do solo, bem como as transformações de curto prazo das substâncias húmicas. Foram utilizadas amostras de Latossolo Vermelho tratadas com seis doses de esterco bovino (0, 5, 10, 20, 40 e 80 t ha-1), as quais foram umedecidas a 60% da capacidade de retenção de água, embaladas em sacos de polietileno, seladas, enterradas no campo a 10 cm de profundidade. Nos tempos 30, 60, 90, 120, 150 e 180 das os sacos foram desenterrados ao acaso e levados para o laboratório. Nas amostras foram determinados o nitrogênio total do solo (Nt), a capacidade de troca de cátions (CTC), o carbono orgânico (CO) total e as frações. No fracionamento foi determinado o teor de carbono nas frações: solúvel em água (C-SA), substâncias húmicas (C-SH), ácidos húmicos (C-AH), ácidos fúlvicos (C-AF) e humina (C-H), pelo método clássico de fracionamento químico. O esterco bovino proporcionou maiores teores de CO total já nas amostras coletadas aos 30 dias a maior parte do C-SH estava presente na forma de humina, seguida por C-AH, e C­AF. Os menores teores de CO ocorreram na fração C-SA. O Nt avaliado aos 180 dias aumentou 0,35 g kg-1 com aplicação de 80 t ha-1 de esterco e a taxa de aumento foi de 0,0043 g kg-1 de N para cada tonelada de esterco aplicada. A CTC aumentou aproximadamente 8 mmolc dm-3 com aplicação de 40 t ha-1 aos 180 dias de incubação / Abstract: Soil organic matter is a primary source of plant nutrients and is considered one of the main indicators of soil sustainability and quality, therefore it is important to know the total organic C (TOC) content, its fractions and the transformations that take place when there is change in soil management. Based on that, this study aimed assessing the effects of fertilization with cattle manure on the contents of total organic carbon, total nitrogen and the cation-exchange capacity of the soil, as well as the short-term transformations of humic substances. Samples of an Haplidox were treated with six doses of cattle manure (O, 5, 10, 20, 40 and 80 t ha-1 dry basis), wetted moisture to 60% of water holding capacity, packaged in polyethylene bags, sealed, buried in the field at 10 cm depth. At 0, 30, 60, 90, 120, 150 and 180 days the bags were randomly unearthed and taken to the laboratory. The samples were analyzed for total soil nitrogen (TSN), cation-exchange capacity (CEC), total organic carbon (TOO ) and their fractions. Upon fractioning, the carbon content in the fractions were determined: water-soluble (WS-C), humic substances (HS-C), humic acids (HA-C), fulvic acids (FA-O) and humin (H-C), through the classical chemical fractioning method. The cattle manure provided higher TOC contents already in the samples collected after 30 days the C-HS was present in the humin, followed by C-HA, and C-FA. The lowest content of C was found in the C-WS fraction. The Nt was assessed at 180 days the increase observed was 0,35 g kg-1 compared to control. The CEC increased approximately 8 mmolc dm-3 with the application of 40 t ha-1 after 180 days / Doutor

Cílem této práce bylo užití termické analýzy, především teplotně modulované diferenční kompenzační kalorimetrie (TMDSC) k odhalení změn ve struktuře huminových kyselin (HA), způsobených pravidelným vlhčením HA vodou a jejím opakovaným sušením. Celkový počet cyklů vlhčení byl pět, neboť následující cykly již nezpůsobily žádné další pozorovatelné strukturální změny. Experimenty provedené v této práci ukázaly, že voda hraje roli nejen v bobtnání struktury HA a přerušení van der Waalsových sil, ale i v přerušení některých vodíkových vazeb, což má větší vliv na snížení teploty skelného přechodu, Tg. Změny v teplotách skelného přechodu byly nepatrné, protože voda ovlivnila především okolí amorfních domén (zodpovědných za skelný přechod), než domény samotné. Dalším úkolem bylo ozřejmit roli volných lipidů ve stabilitě fyzikální struktury HA s ohledem na opakované vlhčení a sušení. Voda periodicky stabilizovala a destabilizovala strukturu HA, ve vzorku HA bez volných lipidů byl vliv vody krátkodobý, voda potřebovala méně času k vyvolání změn ve vzorku, zatímco v původním vzorku byly změny kontinuální. Opakované vlhčení vyvolalo pokles v teplotách fázových přeměn v každém cyklu v porovnání s předcházejícím a ovlivnilo především kinetické procesy, jmenovitě krystalizaci/krystalickou reorganizaci. Opakované vlhčení dále způsobovalo redistribuci a vymytí hydrofilních molekul a tím postupnou hydrofobizaci celé struktury.

[pt] O presente estudo visa a avaliar a efetividade da adição de substâncias húmicas obtidas a partir da destilação de um rejeito de carvão mineral na redução da erodibilidade de um material de desmonte oriundo da mineração de Pedra Miracema. O material de Desmonte empregado no referido estudo é oriundo da extração de rochas ornamentais no município de Santo Antônio de Pádua, situado na região Noroeste do Estado do Rio de Janeiro. O material de desmonte tem textura arenosa e apresenta um teor de argila inferior a 10 por cento e o teor de matéria orgânica praticamente nulo, sendo classificado pelo SUCS como uma areia siltosa, o que lhe confere uma condição de elevada erodibilidade. A fim de reduzir a sua erodibilidade, foram adicionadas diferentes porcentagens de substância húmica proveniente do rejeito de carvão mineral (0 por cento, 0,5 por cento, 1 por cento, 3 por cento, 5 por cento). Adicionalmente, para efeito de comparação se aplicou também 1 por cento de uma substância húmica disponível comercialmente. A erodibilidade da mistura material de desmonte - substâncias húmicas foi avaliada através de um programa de ensaios laboratoriais que incluiu a realização de ensaios de desagregação, ensaios de compressão diametral e ensaios de furo de agulha. Paralelamente, foram realizados com as diferentes misturas ensaios de capacidade de troca catiônica, determinação de teor de matéria orgânica, microscopia ótica e microscopia de eletrônica de varredura a fim de justificar os resultados dos ensaios de avaliação da erodibilidade. Os resultados do programa experimental permitiram sugerir que a incorporação de substâncias húmicas a matriz terrosa do material de desmonte reduz o seu potencial de erodibilidade. Verificou-se ainda que uma maior eficácia do tratamento com o passar do tempo. / [en] This study assessed the effectiveness of humic substances in reducing the erodibility of a quarring waste material from pedra miracema mining. The quarring waste is highly erodible since it possesses a sandy texture, a clay content less than 10 per cent and an organic content close to zero. The humic substance used in the experimental program was obtained from coal waste and it was incorporated to the tailing at the following contents: 0,5 per cent, 1 per cent, 3 per cent and 5 per cent. It was also used a commercial product at 1 per cent content to evaluate the coal was performance. Erodibility was assessed through the use of degradation tests, Brazilian test and pinhole test. Additionally, in order to foster the discussions of the experimental program results, microscopy tests (both optical and electronic), cation exchange capacity and organic matter determinations were performed. The results have shown that the erodibility of the tailing can be reduced by the addition of humic substances. The higher the content the higher the reduction. It was also observed that the performance of humic substances in reducing erodibility increases with time.