A contaminação ambiental provocada pelo despejo de resíduos industriais e pela aplicação de agrotóxicos pode resultar no desequilíbrio dos ecossistemas, além de causar danos diretos à saúde humana. No Brasil, existem várias áreas contaminadas com resíduos industriais, tais como o hexaclorobenzeno (HCB), um composto organoclorado usado no passado como fungicida, mas que atualmente tem seu uso proibido devido a sua alta persistência no ambiente e alta capacidade de bioacumulação. Este estudo verificou a possibilidade de remoção de resíduos de HCB do solo contaminado além da possibilidade de contaminação do ar e da água por este composto. Verificou-se: a) o efeito de adição de matéria orgânica, alteração de pH e alagamento da terra sobre a comunidade microbiana e a degradação do HCB; b) a volatilização do HCB e, c) a lixiviação deste composto. A contaminação inicial da terra foi determinada através de extração das amostras de terra contaminada e análise dos extratos por cromatografia gasosa (CG). Alterações das características da terra foram promovidas pela adição de matéria orgânica (bagaço de cana de açúcar ou vermicomposto), adição de Cal ou alagamento das amostras de terra contaminada, além de combinações destes tratamentos. Cada amostra de terra, colocada em frascos de vidro, recebeu uma solução de HCB radiomarcado (14C-HCB). A mineralização do 14C-HCB foi analisada através da captura do CO2 proveniente das amostras de terra por uma solução de hidróxido de potássio e quantificação do 14CO2 por Espectrometria de Cintilação Líquida (ECL). A volatilização do 14C-HCB foi analisada através da captura dos compostos voláteis por lâmina de poliuretano, extração desta lâmina e análise do extrato por ECL, para quantificação dos 14C-compostos voláteis, e por CG, para quantificação dos compostos voláteis (HCB e metabólitos). A formação de 14C-resíduos ligados e de metabólitos do HCB nas amostras de terra foi analisada através da extração destas amostras e posterior análise da terra extraída por ECL e do extrato por CG. Cada amostra de terra também foi analisada quanto à atividade microbiana, medida através da respiração dos microrganismos, e quanto a densidade microbiana, através da metodologia de contagem de unidades formadoras de colônias (UFC) de bactérias e fungos. A mobilidade e a lixiviação do HCB foram estudadas através de percolação de água em tubos de PVC contendo amostras de terra contaminada tratadas com bagaço de cana de açúcar e/ou cal e solução de 14C-HCB, dispostas sobre amostras de terra não contaminada; os tubos foram seccionados e a terra e a água lixiviada foram analisadas por ECL. O período dos estudos foi de 270 dias. A determinação da contaminação inicial da terra indicou a presença do HCB (3400 mg g-1 terra) e dos metabólitos 1,2,4,5 TCB (24 mg g-1 terra), 1,2,3,4 TCB (6 mg g-1 terra) e PCB (267 mg g-1 terra). A volatilização de 14C-compostos ocorreu em todas as amostras, principalmente nas amostras alagadas e com adição de matéria orgânica (29% a 40 %, após 270 dias). O alagamento favoreceu a volatilização provavelmente devido a baixa hidrossolubilidade do HCB e, a presença de matéria orgânica pode ter favorecido a formação de metabólitos mais voláteis através do estímulo à descloração redutiva, que ocorre sob condições de anaerobiose. Entretanto, a descloração redutiva não foi comprovada pois não houve formação nem aumento na concentração de metabólitos do HCB entre os compostos volatilizados. Houve uma diminuição na quantidade de 14C-compostos extraíveis no decorrer do tempo em todas as amostras, mas a concentração de HCB ou de seus metabólitos permaneceu constante independente do tratamento. A atividade e a densidade microbiana foram maiores nas amostras com bagaço de cana de açúcar mas não tiveram efeito sobre a volatilização ou a degradação do HCB. Não ocorreu mineralização ou mobilidade do 14C-HCB na terra contaminada e nem a formação de 14C-resíduos ligados. Portanto, a adição de matéria orgânica, a alteração de pH e o alagamento da terra não se mostraram eficientes para a remoção do HCB de terra contaminada. Além disso, a ocorrência de formação de 14C-compostos voláteis e a ausência de lixiviação do 14C-HCB indicaram que a presença de resíduos de HCB no solo pode levar à contaminação do ar mas não de água subterrânea. / The environmental contamination by industrial wastes and pesticides can cause harmful effects to ecosystem besides direct human health damages. In Brasil, there are several areas contaminated with industrial wastes like the hexachlorobenzene (HCB), a chlorinated organic compound used in the past as fungicide but that has no longer been produced due to its high persistence in the environment and bioaccumulation potential. This study verified the possibility of HCB residues removal from contaminated soil besides the air and water contamination risk. It was verified: a) the effect of organic matter addition, pH change and flooding of the contaminated soil on the microbial community and HCB degradation; b) HCB volatilization and, c) HCB leaching. The initial soil contamination was determined by extraction of contaminated soil samples and analysis of the extract by Gaseous Chromatography (GC). Soil properties changes were promoted by organic material addition (sugar cane bagasse or earthworm humus), lime addition and flooding of the soil samples besides a combination of these treatments. Each soil sample, placed in glass flasks, was treated with radiolabelled HCB solution (14C-HCB). The 14C-HCB mineralization was analyzed by the entrapment of CO2 originated from the soil samples by potassium hydroxide solution and quantification of the 14CO2 by Liquid Scintillation Spectrometry (LSS). The 14C-HCB volatilization was analyzed by the entrapment of the volatiles compounds by a polyurethane lamina, extraction of this lamina and analysis of the extract by LSS, for 14C-volatile compounds quantification, and by GC, for volatile compounds (HCB and metabolites) quantification. The 14C-bound residues and the HCB metabolites of the soil samples were analyzed by the extraction of these samples and further analysis of the extracted soil by LSS and analysis of the extract by GC. Each soil sample was analyzed with regard to its microbial activity by microbial respiration measure and microbial density by the plate count technique. The mobility and leaching of the HCB were studied by water percolation through PVC tubes containing contaminated soil treated with sugar cane bagasse and/or lime and 14C-HCB placed over no contaminated soil; the tubes were cut in sections and the soil and the leached water were analyzed by LSS. All these studies lasted 270 days. The initial soil contamination determination indicated the presence of the HCB (3400 mg g-1 soil) and the metabolites 1,2,4,5 TCB (24 mg g-1 soil), 1,2,3,4 TCB (6 mg g-1 soil) and PCB (267 mg g-1 soil). The volatilization of the 14C-compounds occurred in all the samples, mainly in the flooded samples with organic matter addition (29% to 40% after 270 days). The flooding enhanced the volatilization due the low HCB water-solubility and, the presence of organic material can have favoured the formation of metabolites more volatile than the HCB due to reductive dechlorination that occurs under anaerobic conditions. But the reductive dechlorination occurrence was not proved as there was no formation or increase in metabolite concentration. There was a decrease in 14C-extractable compounds quantity through the time in all the samples but the HCB and metabolites concentrations keep constant independently of the treatment. The microbial activity and density were higher in the samples with sugar cane bagasse but it did not affected the HCB volatilization or degradation. The 14C-HCB mineralization and the 14C-bound residues formation did not occur. The mobility of the 14C-HCB was not observed too. Therefore, the organic material addition, the pH change and the soil flooding were not efficient to HCB removal from the contaminated soil. And, the occurrence of the volatilization of 14C-compounds and the absence of 14C-HCB leaching indicated that the presence of HCB residues in the soil can result in contamination of air but not the ground water.

The administration of enantiopure drugs brings advantages such as improved efficacy, more predictable pharmacokinetics and reduced toxicity from the point of view of the pharmaceutical area.[1] For this reason, a tremendous amount of supply and demand for enantiomeric pure compounds has been shown not only in market, but industry and academia.[2-4] According to the industry publication Genetic Engineering and Biotechnology News (GEN) in 2014, 22 billion dollars were accounted for enantiopure form of drugs such as Sovaldi® (Sofosbuvir), Crestor® (Rosuvastatin), and Advair® (fluticasone/salmeterol). The fact that one enantiomer can be pharmacologically effective whereas the other enantiomer can be inactive or display non-desirable activity, chiral resolution and asymmetric synthesis research has broken out in recent years to obtain one desired stereoisomer. Enormous amounts of well-organized and rationalized research results for higher enantiomeric selectivity and efficiency has been reported with diverse chiral ligands and transition metals in academia.[5-10] However novelty-driven results from academic area does not meet the requirement in industry field for the practical issue, especially tedious separation process that require high cost and effort. In addition, methodologies developed with privileged chiral ligands and transition metal complexes leave a concern like undesired residue of trace amount of toxic metals in the products. In this dissertation, two types of heterogeneous asymmetric catalyst were investigated to find the alternative that accommodates industrial requirement to obtain enantiomeric pure compounds and novelty-driven academic demands. Firstly, constructions of rationally designed metal organic frameworks (MOFs) using chiral BINOL-derived phosphoric acid ligands were achieved. Overall, catalytic reactions with ocMOFs showed lower enatioselectivity than their homogeneous counterparts, but one of the MOFs, ocMOF-1, was found to exhibit improved enantioselectivity than its homogeneous counterpart in the context of transfer hydrogenation reaction of benzoxazine. Lower enatioselectivity with ocMOFs was rationalized by the chiral environment change by the formation of frameworks in a computational study. In addition, self-supported heterogenization of chiral BINOL-phosphoric acid was achieved by the Yamamoto coupling reaction, and by using catalytically active ocPOP-1 having nanoscopic channels, enantioselectivity was obtained up to 48% in transfer hydrogenation of N-PMP ketimine. Although extension of substituent groups at 3, 3' positions was expected to bring enhanced steric hindrance and to influence to enantioselectivity positively, lack of spatially well-defined interactions induced by this chiral environment change might have lowered the enantiomeric selectivity of the catalytic reaction using ocPOP-1 than its counterpart.

Na capa consta o título "Efeito do processo de compostagem sobre a solubilização e a eficiência agronômica de diferentes fontes de fósforo" / Orientador: Roberto Lyra Villas Bôas / Banca: Dirceu Maximino Fernandes / Banca: Iraê Amaral Guerrini / Banca: Edmar José Kiehl / Banca: Mario Sergio Rodrigues / Resumo: Com o intuito de avaliar o efeito do processo de compostagem sobre a solubilização e a eficiência agronômica de diferentes fontes de fertilizantes fosfatados, foram desenvolvidos dois experimentos. O primeiro constou da produção de compostos orgânicos enriquecidos ou não com superfosfato triplo (ST) ou fosfato natural de Arad (FN). Foi realizado o acompanhamento da temperatura da pilha e do pH do material orgânico durante o processo, além de uma análise química do composto ao final do processo de compostagem. No experimento II, conduzido em vasos com plantas de alface, em casa de vegetação, os compostos orgânicos gerados foram aplicados ao solo para avaliar, através da planta, a Eficiência Agronômica (IEA) do fósforo. Para ambas as fontes, as quantidades de P adicionadas nos vasos foram de 200 mg de P L-1 de terra. Os tratamentos foram: testemunha, fosfato natural de Arad (FN), superfosfato triplo (ST), composto orgânico + ST (COST) com 1,5; 3,0; 4,5 e 6,0% de P, composto orgânico com FN (COFN) com 1,5; 3,0; 4,5 e 6,0% de P adicionada antes da compostagem, COSTF e COFNF com adição das mesmas quantidades de P (ST ou FN) no composto orgânico após o processo de compostagem. Utilizou-se o delineamento estatístico inteiramente casualizado para os dois experimentos. Não se observou no experimento I, efeito favorável do enriquecimento com diferentes porcentagens de superfosfato triplo na compostagem sobre os parâmetros avaliados. Já para adição de diferentes porcentagens de fosfato natural de Arad, observou-se aumento sobre os valores de temperatura, pH, redução da massa da pilha e diminuiu à solubilidade do P solúvel em água, o que sugere que o processo biológico não promoveu a solubilização do fósforo. Para o experimento II os resultados do IEA, baseado na matéria seca e na quantidade de fósforo extraído pela parte aérea... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: To evaluate the composting process on the solubility and agronomic efficiency of different phosphate sources, two experiments were developed. The first consisted of producing organic composts enriched with different levels of triple superphosphate (TS) or natural Arad phosphate (NP). Compost heap temperature and organic material pH were monitored throughout the process; compost chemical analysis was performed at the end of the composting process. In the second experiment, the organic composts were applied to the soil in potted lettuce plants under greenhouse conditions and agronomic phosphate efficiency (APE) was evaluated analysing the plants. For both compost sources, the quantity of additional phosphate was 200mg/L soil. Treatments were: control, NP, TS, organic compost + TS (OCTS) with 1.5, 3.0, 4.5, and 6.0% P, organic compost + NP (OCNP) with 1.5, 3.0, 4.5, and 6.0% P added before composting, OCTSP and OCNPP adding the same quantities of P (NP or TS) after the composting process. A completely randomized experimental design was used for both experiments. No favourable enrichment effects were seen in Experiment I from the different TS levels. However, increase in NP increased temperature and pH, and reduced heap mass and soluble P solubility; this suggests that the biological process did not promote phosphate solubility. APE results from Experiment II, based on dry material and quantity of phosphorous extracted from the above soil part of the lettuce plants, showed that the pre-enrichment composts were inferior to the post-enrichment composts in both crops, indicating that there was no favourable effect in adding TS and NP to the composting process in the evaluated period. / Doutor

The risk of carbon emissions from permafrost is linked to an increase in ground temperature and thus in particular to thermal insulation by vegetation, soil layers and snow cover. Ground insulation can be influenced by the presence of large herbivores browsing for food in both winter and summer. In this study, we examine the potential impact of large herbivore presence on the soil carbon storage in a thermokarst landscape in northeastern Siberia. Our aim in this pilot study is to conduct a first analysis on whether intensive large herbivore grazing may slow or even reverse permafrost thaw by affecting thermal insulation through modifying ground cover properties. As permafrost soil temperatures are important for organic matter decomposition, we hypothesize that herbivory disturbances lead to differences in ground-stored carbon. Therefore, we analyzed five sites with a total of three different herbivore grazing intensities on two landscape forms (drained thermokarst basin, Yedoma upland) in Pleistocene Park near Chersky. We measured maximum thaw depth, total organic carbon content, δ13C isotopes, carbon-nitrogen ratios, and sediment grain-size composition as well as ice and water content for each site. We found the thaw depth to be shallower and carbon storage to be higher in intensively grazed areas compared to extensively and non-grazed sites in the same thermokarst basin. First data show that intensive grazing leads to a more stable thermal ground regime and thus to increased carbon storage in the thermokarst deposits and active layer. However, the high carbon content found within the upper 20 cm on intensively grazed sites could also indicate higher carbon input rather than reduced decomposition, which requires further studies including investigations of the hydrology and general ground conditions existing prior to grazing introduction. We explain our findings by intensive animal trampling in winter and vegetation changes, which overcompensate summer ground warming. We conclude that grazing intensity—along with soil substrate and hydrologic conditions—might have a measurable influence on the carbon storage in permafrost soils. Hence the grazing effect should be further investigated for its potential as an actively manageable instrument to reduce net carbon emission from permafrost.

Die Entwicklung eines Emissionsmoduls für primäres marines Aerosol (PMA; bestehend aus Meersalz und organischem Material) war Hauptgegenstand der vorliegenden Arbeit. Dieses wurde in das Chemie-Transportmodell „COSMO-MUSCAT“ eingebaut und löste dort das vorherige einfach gehaltene Modul (nur Meersalz) ab, welches entsprechend früherer Studien zu hohe Meersalzkonzentrationen berechnete. Das neue Emissionsmodul wurde umfangreich getestet und gegen die Messdaten von verschiedenen Stationen in Europa, einem Bernerimpaktor auf São Vicente (Kap Verden) und einem Aerosolmassenspektrometer sowie einem Digitelfilter während der Fahrt ANT-XXVII/4 des Forschungsschiffes Polarstern validiert. Bei den Untersuchungen kristallisierte sich die Emissionsparametrisierung von Long et al. (2011) als die am Besten geeignete für COSMO-MUSCAT heraus. Weiterhin wurde der Einfluss der Wassertemperatur an der Meeresoberfläche auf die PMA-Emission untersucht. Dabei konnte gezeigt werden, dass dieser Effekt insbesondere für größere Aerosolpartikel (2,5 µm < Dp) relevant ist. Die Nichtbeachtung der Temperaturkorrektur würde in diesem Größenbereich zu einer Überschätzung der Emissionsflüsse und folgend der Konzentration von PMA über kalten Gewässern führen. Beim erstmaligen Vergleich verschiedener Funktionen zur Beachtung des Temperatureffektes erzielte die Funktion von Sofiev et al. (2011) die besten Ergebnisse. Als weitere Neuerung wurde das mit dem PMA emittierte organische Material in das Emissionsmodul eingebaut. Auch hierfür erfolgten Vergleichsstudien verschiedener Parametrisierungen und Ansätze. Allerdings standen nur unzureichende Messungen zur Verfügung, da sie keine Aufteilung in primäres (mit PMA emittiert) und sekundäres (in Gasphase gebildet) organisches Material lieferten. Daher war eine Aussage zur Güte der Funktionen kaum möglich. Die Simulationen zeigten jedoch die Bedeutung der verschiedenen Ansätze zur Berechnung der Emissionsflüsse von organischem Material. So kann bspw. der Einfluss der Emissionsfunktion den Einfluss der Parametrisierung zur Aufteilung in Meersalz und organisches Material deutlich übersteigen. Letztlich bleibt die Frage der richtigen Eingangsdaten für die Emission von primärem organischen Material offen. Es zeigte sich, dass die Abhängigkeit der Anreicherung von organischem Material im PMA von der Chlorophyll a-Konzentration im Oberflächenwasser nicht zwingend gegeben sein muss. Daher ist es notwendig sie in der Berechnung der Emissionsflüsse durch weitere/andere Parameter zu ergänzen/ersetzen. Dies ist Gegenstand eines neuen Forschungsprojektes, bei dem das neue Emissionsmodul angewendet und weiterentwickelt wird.

Made available in DSpace on 2014-06-11T19:22:14Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-01-27Bitstream added on 2014-06-13T19:07:32Z : No. of bitstreams: 1 mobricci_can_me_fca.pdf: 653879 bytes, checksum: e715f421035a5c18fd6084a839fdc6d7 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / O lodo de esgoto (LE) é um resíduo do tratamento das águas servidas, sejam domésticas, industriais ou agroindustriais, contendo níveis de matéria orgânica, macro e micronutrientes fundamentais para a fertilidade do solo. O presente trabalho teve como objetivo estudar o comportamento de plantas de café, comparando a utilização de lodo de esgoto, esterco de curral curtido (EC) e adubação mineral, avaliando-se o desenvolvimento das plantas, alterações na fertilidade do solo e o estado nutricional das plantas, bem como o acúmulo de metais pesados que pudessem atingir concentrações fitotóxicas para o solo e às plantas manejadas com as diferentes doses de lodo de esgoto. O experimento foi instalado em vasos de 20 litros preenchidos com LATOSSOLO VERMELHO. Foi utilizado o cultivar de café Tupi, linhagem IAC 1669-33 como planta indicadora. Constituiu de nove tratamentos e oito repetições, totalizando 72 plantas. Foram avaliados a cada dois meses os parâmetros de altura das plantas e diâmetro da copa. Depois de 12 meses foi avaliada a composição química das folhas fisiologicamente maduras, visando determinar N, P, Ca, Mg, S, Cu, Fe, Mn e Zn e Mo e os metais pesados As, Cd, Cr, Hg, Pb, Ni e Se. No mesmo período foram retiradas amostras de solo das parcelas, onde quatro amostras simples foram homogeneizadas, secas ao ar e peneiradas para posteriormente ser retirada uma amostragem composta para se determinar os nutrientes. As médias das características foram avaliadas pelo quadro de análise de variância (ANAVA) e regressão linear múltipla e comparadas pelo Teste de Tukey a um nível de 5% de significância. Os resultados comprovam a eficiência do lodo de esgoto no fornecimento de nutrientes às plantas de café, principalmente, N, P, Ca, Mg, Mo, Cu, Zn e na redução da acidez ativa e potencial dos solos. A elevação do pH e o aumento dos teores de 2 matéria orgânica... / The sewage sludge is a residue of served water treatment (domestic, industrial or agoindustrial water), with organic material levels and basic macro and micronutrients for the soil fertility. This work had the aim of studying the behavior of coffee plants, comparing the sewage sludge, corral manure and mineral fertilization usage, evaluating the plants development, soil fertility alterations and plants nutritional state, as well the accumulation of heavy metal which could reach biotoxic concentrations for the soil and plants treated with the different doses of sewage sludge. The experiment had been installed in 20 liters vases filled with RED LATOSSOIL. It had been used Tupi Coffee, ancestry IAC 1669-33 as indicator plant. The experiment had been constituted of 9 treatments and 8 replications, totaling 72 plants. The biometrics parameters of plants had been evaluated in each 2 months, as plants height, cop diameter. After 12 months, the chemical compound of physiological mature leaves had been evaluated, aiming to determine N, P, Ca, Mg, S, Cu, Fe, Mn Zn, Mo and the heavy metals As, Cd, Cr, Hg, Ni, Pb and Se. In the same period, soil samples had been removed from the plots, in which 4 simple samples had been homogenized, dried in air and sifted, and later, compound samples had been removed to determine the nutrients. The averages of the characteristics had been evaluated by the variation analysis chart (ANAVA) and multiple linear regression and compared by the Tukey Test, with 5% significance level. The results prove the efficiency of sewage sludge to provide nutrients to coffee plants, mainly N, P, Ca, Mg, Mo, Cu, Zn and reduce the active and potential acidity of soils. The pH elevation and organic material tenors increase provided by the sewage sludge and corral manure treatments conduced a smaller mobility of heavy metals in soils and leaves, 4 not reaching critical levels to the environment or to the coffee plants.

Att man förstår mark- och grundvattenflöde är en förutsättning för förståelsen av ämnestransport genom skogsmark. Ståndortskarteringen har inte möjlighet att mäta grundvattenflödet på sina provytor med t ex totalpotentialmätningar utan behöver en alternativ metod. Syftet med detta arbete var att skapa en multivariat klassificeringsmodell för klassificering av grundvattenförhållandena i en skogssluttning söder om Tärnsjö i norra Uppland. Modellen bygger på principalkomponentanalys av olika kemiska variabler i det fasta organiska materialet i den organiska horisonten. De kemiska variablerna som användes var; pH(H2O), pH(BaCl2), andel C, S och N i det organiska materialet, den procentuella andelen Al3+, H+, Ca2+, Mg2+, K+ och Na+ på utbyteskomplexen, CECeff och andel organiskt material i proven. Principalkomponentanalysen tyder på att (1) inströmningsområdet karaktäriserades av lågt pH, låga Na+-halter och relativt höga K+-halter, (2) det omättade utströmningsområdet karaktäriserades av höga Al3+-halter, och (3) det näst intill mättade utströmningsområdet karaktäriserades av höga Na+-, Ca2+- och Mg2+-halter som gav högre pH-värden samt högre andel av S och N i det organiska materialet. Undersökningen tyder på att grundvattenförhållandena i en barrskogssluttning har stor betydelse för de kemiska egenskaperna hos markens organiska horisont. Informationen man får från markkemiska analyser gör det möjligt att med hjälp av kemiska variabler klassificera graden av in- respektive utströmningsförhållanden. Den multivariata klassificeringsmodell som skapades i denna undersökning ger en riktlinje för hur en generell klassificeringsmodell för indikationer av grundvattenförhållanden kan konstrueras. Den generella klassificeringsmodellen är ett alternativ till t ex totalpotentialmätningar eftersom klassificeringsmodellen varken behöver ske på plats eller mätas i tidsserier. Vidare kan klassificeringsmodellen tillämpas på redan existerande markkemiska analyser. / A thorough understanding of soil water and groundwater flow is necessary to understand the transport of elements in forest soils. The National Forest Soil and Vegetation Survey has no possibilities to determine groundwater flow using total potential measurements in the sampling plots. In the present work an alternative approach using soil chemistry to classify the extent of recharge and discharge conditions in the sampling plots was used. A multivariate model was created to classify groundwater regime in a forested hillslope south of Tärnsjö in the northern part of Uppland, Sweden. The model was based on principal component analysis (PCA) of different variables in solid organic matter in the organic horizon in the soil. The chemical variables used were pH(H2O), pH(BaCl2), total C, N and S in organic matter, the percentage of Al3+, H+, Ca2+, Mg2+, K+, Na+ in the exchange complex, the effective CEC and the percentage of organic matter in the soil samples. PCA indicated that; (1) samples from the recharge area were characterised by low pH, low Na+ and relatively high K+ levels, (2) the unsaturated discharge zone was characterised by high levels of exchangeable Al3+ and (3) the nearly saturated discharge area was characterised by high Na+, Ca2+ and Mg2+ levels, higher pH and higher amounts of N and S in the organic matter. This study indicated that groundwater regime in a forested hillslope is of major importance in determining the chemical status of the organic matter in the organic horizon. It was possible to use information obtained from soil chemical analysis to determine the extent of recharge or discharge at the points where the soil samples were taken. The PCA model used in this work gives guidelines for the construction of a general model for classification of groundwater regimes.

This PhD work was devoted to the understanding of the laser-induced plasma on organic materials and theapplication of laser-induced breakdown spectroscopy (LIBS) to quantitative analysis of these materials. Itcontributes to deepen our knowledge on the physical mechanisms involved in laser-matter interaction, plasmageneration, evolution and expansion of the plasma into the ambient gas, with emphasis on plasmas induced onorganic targets. It also intends to improve the performance of LIBS for the analysis of organic materials. Thespecificity for organic targets fits the current focus of the international community working on LIBS, toimprove the control of the plasma induced on this kind of material which has a distinguished optical prosperitywith respect to that of metals, better known for laser ablation. It addresses also the growing need to apply theLIBS technique to organic materials for different applications in the environmental, food, or biomedicaldomains. The works in this thesis were therefore presented in this thesis document according to the followingorganization.After the General Introduction which introduces the scientific and technological contexts, Chapter Irecalls the basic theoretical elements necessary to understand the phenomenon of plasma generation by laserablation, and its evolution in the background gas. Ablation of organic material is emphasized. Procedures andtechniques of diagnostics of laser-induced plasma were then presented with a focus on the transient andinhomogeneous nature of the expanding plasma. Chapter II focuses on the generation and the evolution of theplasma induced on the skin of a potato, a typical sample of agricultural product. The characteristics of plasmainduced on a soft and wet organic target, such as a fresh potato, was something unknown when the thesis workstarted. These characteristics provide the necessary basis for the quantitative analysis of the trace andultra-trace metallic elements in these samples. Following this characterization, semi-quantitative analyticalresults were extracted from LIBS spectra corresponding to potato skin. Chapter III is presented in thecontinuity of Chapter II for the application of LIBS to the quantitative analysis of organic materials. Acomparative study on the analytical results with LIBS and ICP-AES for milk powders allows an assessment ofthe performances of quantitative analysis by LIBS for organic materials, and a validation of the CF-LIBSprocedure that we have developed. Different from Chapters II and III where attention was paid to trace metalelements, Chapter IV studies the behavior of the major elements that make up the matrix of organic material,which are 4 known organic elements: H, C, O, N. During the decomposition of organic material by laserablation, these elements can be found in the form of molecular fragments, or recombined into molecularspecies. We then study in this Chapter the evolution of these species as a function of the laser ablationparameters, the laser wavelength in particular. The thesis document ends with a general conclusion andoutlooks.

Resumo: Gerbera jamesonii Bolus é uma espécie da família Compositae. O capítulo, com diâmetro de 8 - 14 cm, possui flores liguladas de cores vivas organizadas ao redor do centro, que contém os botões florais. Esta inflorescência é sustentada por uma haste longa e sem folhas. Atualmente é uma das dez flores mais comercializadas no Brasil e está entre as três principais flores de corte. A utilização de soluções conservantes, tratamentos de "pulsing", ou fortalecimento, e baixas temperaturas de armazenamento visa prolongar a vida e manter por mais tempo a qualidade das flores cortadas. Neste contexto, este trabalho teve por objetivos avaliar o efeito de diferentes práticas de manejo na pós-colheita sobre a fisiologia e conservação de inflorescências de gérberas. Para os quatro primeiro experimentos foi utilizada a gérbera cv. Suzanne, de coloração laranja. Os experimentos foram conduzidos em delineamento inteiramente casualizado, em esquema fatorial. No primeiro experimento, as inflorescências permaneceram nas seguintes soluções de manutenção: 1) Água destilada; 2) Cloro a 100 mg.L-1; 3) 8-hidroxiquinolina (8-HQC) a 100 mg.L-1; 4) 8-HQC a 200 mg.L-1; e 5) 8- HQC a 400 mg.L-1, cujas hastes foram mantidas em condição controlada de laboratório (20°C; 70% UR). Este experimento possibilitou observar danos nas bases das hastes, causados pelos tratamentos com cloro a 100 mg.L-1 e com as doses mais elevadas de 8-HQC. A manutenção da boa qualidade foi observada no tratamento com 8-HQC a 200 mg.L-1. A longevidade média foi de 12 dias em vaso. No segundo experimento foram utilizadas, durante o armazenamento a 20°C e 70% UR, as soluções: 1) Água destilada; 2) Ácido cítrico a 64 g.L-1; 3) Cloro a 25 mg.L-1 4) Cloro a 50 mg.L-1 5) 8-HQC a 25 mg.L- 1 e 6) 8-HQC a 50 mg.L-1. Com os resultados verificou-se a baixa eficiência do... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Gerbera jamesonii belongs to the Compositae family. The inflorescence, with diameter of 8 - 14 cm, is a capitulum with ligules with vivid color organized around de center, that contain flower buds, which can be in a variety of colors. This colorful flower is supported by a long stem, without leaves. Nowadays it is one of the ten most commercialized flowers in Brazil and is one of the three main cut flowers. The use of keeping-quality solutions, pulsing treatments and low temperature during the vase life seeks to prolong vase life and to maintain the quality of cut flowers. In this context, this research was conducted, at FCAV-UNESP, Jaboticabal, SP, Brazil, to evaluate the effects of several handling techniques on postharvest physiology gerbera cut flowers. The experiments followed complete randomized design, in factorial arrangement. On the first one, the inflorescences remained in the following solutions: 1) Distilled water; 2) Chlorine at 100 mg.L-1; 3) 8-hydroxyquinolin (8-HQC) at 100 mg.L-1; 4) 8-HQC at 200 mg.L-1; and 5) 8-HQC at 400 mg.L-1, which the stems remained in environmental conditions (20°C; 70% RH). On this experiment, it was possible to observe the damage caused by the treatments using chlorine at 100 mg.L-1 and high dosage of 8-HQC. The good quality where kept by using 8-HQC at 200 mg.L-1 and the average longevity of the experiment was 12 days. On the second experiment, the gerberas remained, during storage, in the following solutions: 1) Distilled water; 2) Citric acid at 64 g.L-1; 3) Chlorine at 25 mg.L-14) Chlorine at 50 mg.L-1; 5) 8-HQC at 25 mg.L-1 ; and 6) 8-HQC at 50 mg.L-1. With the results it was possible to verify the low efficiency of the citric acid at the used concentration and the lower damage by lower concentrations of chlorine and 8-HQC than the usually recommended, which kept the good quality of the flowers for... (Complete abstract, click electronic access below) / Orientador: Ben-Hur Mattiuz / Coorientadora: Teresinha de Jesus Deléo Rodrigues / Banca: Regina Maria Monteiro de Castilho / Banca: Carlos Eduardo Ferreira de Castro / Banca: Káthia Fernandes Lopes Pivetta / Banca: Pedro Luís da Costa Aguiar Alves / Doutor

Orientador: Hélio Grassi Filho / Banca: Leandro Borges Lemos / Banca: Carlos Henrique dos Santos / Resumo: O lodo de esgoto (LE) é um resíduo do tratamento das águas servidas, sejam domésticas, industriais ou agroindustriais, contendo níveis de matéria orgânica, macro e micronutrientes fundamentais para a fertilidade do solo. O presente trabalho teve como objetivo estudar o comportamento de plantas de café, comparando a utilização de lodo de esgoto, esterco de curral curtido (EC) e adubação mineral, avaliando-se o desenvolvimento das plantas, alterações na fertilidade do solo e o estado nutricional das plantas, bem como o acúmulo de metais pesados que pudessem atingir concentrações fitotóxicas para o solo e às plantas manejadas com as diferentes doses de lodo de esgoto. O experimento foi instalado em vasos de 20 litros preenchidos com LATOSSOLO VERMELHO. Foi utilizado o cultivar de café Tupi, linhagem IAC 1669-33 como planta indicadora. Constituiu de nove tratamentos e oito repetições, totalizando 72 plantas. Foram avaliados a cada dois meses os parâmetros de altura das plantas e diâmetro da copa. Depois de 12 meses foi avaliada a composição química das folhas fisiologicamente maduras, visando determinar N, P, Ca, Mg, S, Cu, Fe, Mn e Zn e Mo e os metais pesados As, Cd, Cr, Hg, Pb, Ni e Se. No mesmo período foram retiradas amostras de solo das parcelas, onde quatro amostras simples foram homogeneizadas, secas ao ar e peneiradas para posteriormente ser retirada uma amostragem composta para se determinar os nutrientes. As médias das características foram avaliadas pelo quadro de análise de variância (ANAVA) e regressão linear múltipla e comparadas pelo Teste de Tukey a um nível de 5% de significância. Os resultados comprovam a eficiência do lodo de esgoto no fornecimento de nutrientes às plantas de café, principalmente, N, P, Ca, Mg, Mo, Cu, Zn e na redução da acidez ativa e potencial dos solos. A elevação do pH e o aumento dos teores de 2 matéria orgânica... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The sewage sludge is a residue of served water treatment (domestic, industrial or agoindustrial water), with organic material levels and basic macro and micronutrients for the soil fertility. This work had the aim of studying the behavior of coffee plants, comparing the sewage sludge, corral manure and mineral fertilization usage, evaluating the plants development, soil fertility alterations and plants nutritional state, as well the accumulation of heavy metal which could reach biotoxic concentrations for the soil and plants treated with the different doses of sewage sludge. The experiment had been installed in 20 liters vases filled with RED LATOSSOIL. It had been used Tupi Coffee, ancestry IAC 1669-33 as indicator plant. The experiment had been constituted of 9 treatments and 8 replications, totaling 72 plants. The biometrics parameters of plants had been evaluated in each 2 months, as plants height, cop diameter. After 12 months, the chemical compound of physiological mature leaves had been evaluated, aiming to determine N, P, Ca, Mg, S, Cu, Fe, Mn Zn, Mo and the heavy metals As, Cd, Cr, Hg, Ni, Pb and Se. In the same period, soil samples had been removed from the plots, in which 4 simple samples had been homogenized, dried in air and sifted, and later, compound samples had been removed to determine the nutrients. The averages of the characteristics had been evaluated by the variation analysis chart (ANAVA) and multiple linear regression and compared by the Tukey Test, with 5% significance level. The results prove the efficiency of sewage sludge to provide nutrients to coffee plants, mainly N, P, Ca, Mg, Mo, Cu, Zn and reduce the active and potential acidity of soils. The pH elevation and organic material tenors increase provided by the sewage sludge and corral manure treatments conduced a smaller mobility of heavy metals in soils and leaves, 4 not reaching critical levels to the environment or to the coffee plants. / Mestre