De nos jours, la contamination des sols par les polluants organiques et inorganiques est une problématique majeure. Des techniques douces de remédiation, reposant sur l’utilisation de plantes et de microorganismes, associés à des amendements ou non, sont étudiées pour gérer ces sols. Parmi les différents amendements, le biochar est présenté dans la littérature comme pouvant répondre à ces attentes. Ce travail se propose d’évaluer l’impact des paramètres de pyrolyse sur les caractéristiques de huit biochars élaborés à partir de Miscanthus x giganteus, cultivé sur un sol contaminé en métaux, et de sélectionner le(s) biochar(s) susceptible(s) d’être le(s) plus performant(s) en termes de remédiation de sols contaminés en métaux (Cd, Pb, Zn) et/ou HAP. Il a été mis en évidence une forte influence de la température de pyrolyse sur les caractéristiques des biochars. De plus, les biochars ont présenté de fortes capacités de sorption des trois métaux et des HAP en solution, notamment pour les biochars produits à 600°C. Des expérimentations réalisées avec un sol artificiel et une terre agricole contaminés artificiellement ont mis en évidence la capacité de certains biochars à diminuer la disponibilité environnementale, la biodisponibilité et la bioaccessibilité orale des métaux et des HAP. Sur la base des résultats obtenus, un biochar a été sélectionné comme répondant le mieux aux attentes en termes de gestion de sols multicontaminés. Compte tenu des modifications structurelles du biochar dans les sols, il conviendrait de valider ces résultats sur le long terme, en condition in situ, tout en s’assurant de l’innocuité du biochar étudié et en intégrant les aspects socio-économiques. / Nowadays, soil contamination by the organic and inorganic pollutants represent a major issue. Gentle remediation options, comprising plants and microorganisms, and linked with the use of amendments or not, are implemented to manage these soils. Among the different amendments, the biochar is presented in the literature as being able to meet these expectations. This study aims at evaluating the impacts of pyrolysis parameters on the characteristics of eight biochars derived from Miscanthus x giganteus, grown on metal contaminated soils, and selecting the one which may be the most efficient to remediate metals (Cd, Pb, Zn) and/or PAHs contaminated soils. A strong influence of pyrolysis temperature on biochar characteristics was detected. Moreover, biochars showed strong sorption capacity for the three metals and PAHs in aqueous solution, especially for those produced at 600°C. Experiments realized with an artificial soil, and an agricultural soil, both artificially contaminated, demonstrated the efficiency of some biochars to decrease the environmental availability, bioavailability and oral bioaccessibility of the metals and PAHs. Based on the results, one biochar was selected as being the most efficient to manage the contaminated soils. In view of the structural modifications of biochars in soils, these results should be validated in situ on long term basis, while ensuring the harmless effects of the studied biochar and integrating the socio-economic aspects.

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Made available in DSpace on 2018-08-01T22:33:09Z (GMT). No. of bitstreams: 1 tese_8995_Cristiane Francisca Barbosa.pdf: 1390114 bytes, checksum: 618f0bde8a50c7e3ee2bedb6b6c10580 (MD5) Previous issue date: 2016-08-31 / Biocarvão é o produto da decomposição térmica de materiais orgânicos sob baixa concentração de oxigênio e em temperaturas controladas. Os benefícios agronômicos e ambientais do seu uso estão associados a temperatura de pirólise e a matéria prima utilizada para o seu processamento. Este estudo teve por objetivo avaliar a influência da matéria prima e da temperatura de pirólise na caracterização final do produto e nas alterações de suas características químicas e físicas. Para isso, os biocarvões foram provenientes de duas temperaturas (350 °C e 600 °C) e dois resíduos (palha de café - PC e casca de eucalipto - CE). O processo de pirólise lenta foi realizado em um reator metálico de leito fixo hermeticamente fechado, com tempo de permanência do material na temperatura final de 60 minutos. Os rendimentos em biocarvão, bio-óleo e gases foram quantificados e nos biocarvões foram determinados: os teores elementares de carbono (C), hidrogênio (H), nitrogênio (N) e oxigênio (O), pH, capacidade de troca catiônica (CTC), teor de cinzas (Cz) e de nutrientes (Ca, Mg, K e P). As mudanças morfológicas decorrentes do processo de pirólise foram investigadas por microscopia eletrônica de varredura (MEV). Determinou-se a densidade aparente (Da) pelo método da proveta, e a capacidade de retenção de água dos biocarvões a (- 33kPa) em extrator de placa porosa. Os resultados experimentais mostraram que a pirólise da CE a temperatura de 350 °C proporcionou maior rendimento em biocarvão. O tipo de matéria prima não influenciou os teores de C dos biocarvões, apenas os teores de H, O e N. Biocarvões obtidos da PC apresentaram maiores teores de Mg, P e K, maior CTC e pH mais alcalino. Biocarvões de CE apresentaram maiores teores de Ca e cinzas. A pirólise a 600 °C obteve biocarvões com maior relação C/N, menores teores de H, N e O, menor CTC, maior teor de cinzas e nutrientes, pH mais alcalino e maior aromaticidade. A análise de espectroscopia de Infravermelho por Transformada de Fourier (FTIR) evidenciou uma diminuição de grupos funcionais e aumento de grupos aromáticos com a elevação da temperatura. As micrografias de MEV demonstraram que os biocarvões obtidos a 600 °C apresentaram poros mais desenvolvidos, com menor espessura da parede e maior desarranjo estrutural. A densidade dos biocarvões variou em função da matéria prima utilizada, os biocarvões de CE apresentaram maior densidade, em relação aos de PC.

Water pollution is one of the major ecological threats people face around the world. Water contamination by organic and inorganic compounds is hazardous to both the environment and human health. Adsorption techniques have gained much attention in the field of water remediation due to their efficiency, simplicity in operation, and ease of implementation. However, the adsorbents currently being used are costly. The main objective of this work is to develop novel, low-cost adsorbents from waste material by modifying the adsorbent surface for water remediation. Adsorbent modifications involve various chemical and physical methods such as acid/base treatments, metal/metal oxide impregnation, functional group alteration, and steam/air activation. In chapter I, these modification methods are summarized along with characterization techniques and adsorption interactions available for contaminant removal. In chapter II, a novel activated carbon is introduced from the fruit of Garcinia cambogia with acid activation, for the removal of Pb(II) and Cd(II) from water. Activated carbon was prepared by soaking dried Garcinia cambogia pieces in 85% phosphoric acid and carbonizing at 650 °C in a muffle furnace for 1 h. Chapter III describes the modification of waste tire rubber as an adsorbent for heavy metal ion removal. This modification was done by mixing ground tire rubber (GTR) with chitosan dissolved acetic acid (2%) solution followed by NaOH treatment. Chitosan modified-GTR successfully removed more Pb(II) and Cu(II) ions than GTR, suggesting added amine groups on the GTR surface through chitosan modification enhanced the heavy metal ion adsorption. In chapter IV, caffeine, ibuprofen, and acetylsalicylic acid removals by hybrid magnetic Fe3O4/Douglas fir biochar adsorbent are discussed. Adsorptions were compared with non-magnetic Douglas fir biochar. The surface chemistry and composition of modified adsorbents were examined by SEM, SEM-EDX, TEM, PZC, XRD, XPS, FTIR, TGA, elemental analysis, and surface area measurements.

Soil biochar application effects in agricultural systems are not well understood. Corn (Zea mays L.), soybean (Glycine max L.), wheat (Triticum aestivum L.), cereal rye (Secale cereal L.), and alfalfa (Medicago sativa L.) were grown on two soils amended with four rates of biochar, a Marietta fine sandy loam (fine-loamy, siliceous, active, thermic Fluvaaquentic Eutrudept) and a Houston silty clay (very fine, smectitic, thermic Oxyaquic Haplaudert) and allowed to equilibrate for 56 days. To investigate a possible nitrogen effect, three nitrogen rates were added to non-legume species. Our results revealed reductions in nutrient uptake across all crops, but this followed the same trend as shoot dry weight production and plant tissue concentration for pots treated with biochar. The significant reduction in uptake and tissue concentration are believed to be linked to smaller plant sizes. Therefore, it is believed that biochar applications are not having an effect on plant growth.

Little is known about the effect of biochar created from poultry litter on soil properties and plant growth. Five studies were conducted using biochar made by the fast pyrolysis of poultry litter. Two were greenhouse studies and three were field studies. The greenhouse studies were conducted with a sandy loam soil and a silt loam soil. First, lettuce (Lactuca sativa L) seeds were germinated in the greenhouse across biochar incorporation rates from 0 to 100%, and secondly a trial was conducted in which green peppers (capsicum annum L) were grown in soils with up to 5% biochar by weight. Elemental analysis was completed on the biochar and the soils were analyzed for bulk density (BD), water holding capacity (WHC), pH, cation exchange capacity (CEC), soluble salts (SS) and extractable nutrients. The field studies all used the rates of 0, 4.5, and 9 Mg ha-1 biochar and the rates were applied in the early spring of 2009 and 2010. Biochar was surface applied on a tall fescue pasture [Lolium arundinaceum (Schreb.) Darbysh. (=Festuca arundinacea Schreb. subsp. arundinacea)] and tilled in on two green pepper field sites. The soils were analyzed for carbon (C) content, pH, CEC, Mehlich 1 P, and SS. No significant difference was found in yields at any of the three sites, but differences in forage quality were found. Biochar made from poultry litter showed several benefits as a soil amendment in all the studies, but application rates would be limited by soil test P and pH. / Master of Science

A aplicação de biocarvão ao solo tem sido divulgada como prática com vantagens agrícolas e ambientais. Devido à sua elevada reatividade, o biocarvão pode interagir com contaminantes orgânicos e inorgânicos do solo, diminuindo o potencial poluidor de elementos tóxicos e pesticidas. Contudo, a eficácia de herbicidas pré-emergentes pode ser anulada devido à presença de biocarvão no solo, o que impõe a necessidade de doses maiores e resulta no aumento do risco de contaminação ambiental. Adicionalmente, pode haver maior persistência de pesticidas no solo devido à retenção e menor disponibilidade das moléculas em solos com biocarvão. As reações que ocorrem entre o biocarvão e os pesticidas dependem das próprias características do solo e da molécula, além do tempo de interação com o solo (aging) e das propriedades intrínsecas ao biocarvão (biomassa de origem, T°C de pirólise e granulometria). O tebuthiuron e a hexazinona são herbicidas com elevado potencial de lixiviação e podem ter seu destino alterado em função da presença de biocarvão no solo. Estas moléculas possuem elevado tempo de meia-vida (t1/2) e biodegradam lentamente no ambiente edáfico. Assim, processos oxidativos avançados (POA) podem acelerar a decomposição dos herbicidas, sendo ainda uma maneira de integrar o biocarvão em processos químicos para a dissipação de poluentes. Objetivou-se avaliar os efeitos da aplicação de biocarvão na dinâmica dos herbicidas tebuthiuron e hexazinona em solos, tendo-se como objetivos específicos: i) verificar o comportamento sortivo desses herbicidas frente à aplicação de biocarvões produzidos a partir de diferentes matérias-primas e T°C de pirólise, incluindo a influência de fatores como o aging dos herbicidas no solo, tamanho das partículas do biocarvão e disponibilidade de carbono orgânico dissolvido (COD) no solo promovida pela adição do biocarvão; ii) avaliar se a interação entre os herbicidas e o biocarvão afeta a eficiência de controle de braquiária (Brachiaria decumbens); iii) analisar a influência do biocarvão na dissipação e lixiviação de tebuthiuron e hexazinona; e iv) identificar o potencial de uso do biocarvão em POA, como suporte para catalisadores metálicos heterogêneos e como fonte de ferro para reações de Fenton, bem como avaliar o desempenho destes materiais na catálise oxidativa de hidrocarbonetos e dos herbicidas. Experimentos de sorção, (verificando a influência de biocarvões de diferentes matérias-primas e T°C de pirólise, aging e granulometria, além da avaliação em solos de texturas contrastantes), bem como de dissipação e lixiviação foram conduzidos, utilizando-se herbicidas radiomarcados. Em paralelo, a liberação de COD pelos biocarvões e pelos solos foi quantificada, enquanto que um experimento de eficiência de controle sobre braquiária em casa de vegetação foi conduzido. Os biocarvões foram, ainda, avaliados quanto ao potencial de uso como suporte para catalisadores metálicos e para reações de Fenton, avaliando-se sua performance para a oxidação dos herbicidas e de hidrocarbonetos. Apesar de não alterar a classe de lixiviação de tebuthiuron e hexazinona em curto prazo, quando considerado o efeito do aging, a presença de biocarvão de palha de cana-de-açúcar 550°C (PC550) no solo, independentemente da granulometria, pode auxiliar no manejo de herbicidas com elevada mobilidade, especialmente em solos de textura arenosa e com baixo teor de carbono. Neste caso, o herbicida tebuthiuron teve sua classificação alterada de \"molécula lixiviável\" (Kd,app < 5,0 L kg-1) para \"molécula não-lixiviável\" (Kd,app > 5,0 L kg-1). No entanto, o biocarvão de dejeto de galinha 350°C (DG350) aumenta o COD do solo, resultando na diminuição da sorção dos herbicidas. A adição dos biocarvões PC550 e DG350 ao solo não modificam a eficiência de controle de braquiária por moléculas altamente solúveis. Doses a partir das doses recomendadas em campo promovem controle eficiente, independentemente da presença ou não de biocarvão no solo. Tebuthiuron e hexazinona são moléculas recalcitrantes no ambiente, sendo muito baixas suas taxas de mineralização e de dissipação, tanto na presença como na ausência dos biocarvões PC550 e DG350. A presença de biocarvão no solo pouco influenciou a dissipação dessas moléculas. Os biocarvões PC550 e DG350 diminuem o potencial de lixiviação da hexazinona no solo de textura areia franca, mas não afetam o movimento vertical do tebuthiuron nas mesmas condições. Apesar do menor potencial para degradação de tebuthiuron e hexazinona em relação à epoxidação de hidrocarbonetos, a inserção do biocarvão para a síntese de catalisadores mostrou-se eficiente e permitiu o emprego deste material em processos de catálise industrial e ambiental, podendo auxiliar para o manejo da remediação de poluentes e contribuindo para expandir o uso do biocarvão. / Biochar amendments to soil has been claimed as a practice with agricultural and environmental advantages. Due to its high reactivity, biochar can interact with organic and inorganic soil contaminants, reducing the pollution potential of toxic elements and pesticides. However, pre-emergent herbicides efficacy can be negatively affected by biochar additions to the soil, which may impose higher doses and increase the environmental contamination risk. In addition, there may be increasing in the pesticide\'s persistence due to retention and lower availability of the molecules induced by biochar amendment to the soil. The interactions between biochar and the pesticides depend on the characteristics of the soil and the herbicide itself, besides the aging and the biochar\'s properties (biomass, pyrolysis T°C and granulometry). Tebuthiuron and hexazinone are herbicides with leaching potential and may have their fate modified due to the presence of biochar in the soil. These molecules have a high half-life time (t1/2) and biodegrade slowly in the environment. Thus, advanced oxidative processes (AOP) can accelerate the decomposition of herbicides and can be a way of incorporate biochar in chemical processes towards pollutants dissipation. We aimed to evaluate the effects of biochar amendments on tebuthiuron and hexazinone dynamics in soils, and the specific objectives were: i) to verify the sorption behavior of these herbicides in response to biochar\'s amendment from different feedstock and pyrolysis T°C, including the influence of factors such as herbicide aging on the soil, biochar particle size and availability of dissolved organic carbon (DOC) in the soil promoted by biochar addition; ii) to evaluate if the interaction between the herbicides and the biochars affects braquiária (Brachiaria decumbens) control efficiency; iii) to analyze the biochars influence on the dissipation and leaching of tebuthiuron and hexazinone; and iv) to identify the potential use of biochar in AOP as heterogeneous metal catalysts support and as a source of iron for Fenton reactions, as well as to evaluate the performance of these materials in oxidative catalysis of hydrocarbons and herbicides. Sorption experiments, (checking the influence of biochars from different feedstocks and pyrolysis T°C, aging and granulometry, as well as accessing the differences among soil textures), and dissipation and leaching experiments were conducted using radiolabeled herbicides. In parallel, the release of DOC by the biochars and soils was quantified, whereas an experiment in a greenhouse for braquiária control was conducted. The biochars were also evaluated for use as metal catalysts supports and for Fenton reactions, evaluating their performance for herbicides and hydrocarbons oxidation. Although it does not change tebuthiuron and hexazinone leaching class in short term, when considering the aging, the sugarcane straw biochar pyrolyzed at 550°C (PC550), regardless of granulometry, may be useful in the management of high mobility herbicides, especially in sandy soils with low carbon content. In this case, tebuthiuron had its classification modified from \"leachable\" (Kd,app < 5.0 L kg-1) for \"non-leachable\" molecule (Kd,app > 5.0 L kg-1). However, the biochar from poultry manure pyrolyzed at 350°C (DG350) increases the DOC content in the soil, resulting in decreased sorption of the herbicides. The additions of PC550 and DG350 to the soil does not modify the control efficiency of braquiária by highly soluble molecules. Doses higher than the recommended ones promote efficient control, regardless of the presence or absence of biochar in the soil. Tebuthiuron and hexazinone are highly recalcitrant molecules in the environment, having low rates of mineralization and dissipation both in the presence or absence of the biochars PC550 and DG350. The biochar application to the soil barely influenced the herbicides dissipation. The biochars PC550 and DG350 decrease the leaching potential of hexazinone in the sandy soil, but do not affect tebuthiuron leaching in the same conditions. Despite the lower potential for tebuthiuron and hexazinone degradation in relation to the epoxidation of hydrocarbons potential, biochar insertion in the synthesis of catalysts has been proved to be efficient, allowing the use of these wastes in industrial and environmental catalysis processes for pollutants remediation purposes and helping to expand the biochar range of uses.

A aplicação de biocarvão ao solo tem sido divulgada como prática com vantagens agrícolas e ambientais. Devido à sua elevada reatividade, o biocarvão pode interagir com contaminantes orgânicos e inorgânicos do solo, diminuindo o potencial poluidor de elementos tóxicos e pesticidas. Contudo, a eficácia de herbicidas pré-emergentes pode ser anulada devido à presença de biocarvão no solo, o que impõe a necessidade de doses maiores e resulta no aumento do risco de contaminação ambiental. Adicionalmente, pode haver maior persistência de pesticidas no solo devido à retenção e menor disponibilidade das moléculas em solos com biocarvão. As reações que ocorrem entre o biocarvão e os pesticidas dependem das próprias características do solo e da molécula, além do tempo de interação com o solo (aging) e das propriedades intrínsecas ao biocarvão (biomassa de origem, T°C de pirólise e granulometria). O tebuthiuron e a hexazinona são herbicidas com elevado potencial de lixiviação e podem ter seu destino alterado em função da presença de biocarvão no solo. Estas moléculas possuem elevado tempo de meia-vida (t1/2) e biodegradam lentamente no ambiente edáfico. Assim, processos oxidativos avançados (POA) podem acelerar a decomposição dos herbicidas, sendo ainda uma maneira de integrar o biocarvão em processos químicos para a dissipação de poluentes. Objetivou-se avaliar os efeitos da aplicação de biocarvão na dinâmica dos herbicidas tebuthiuron e hexazinona em solos, tendo-se como objetivos específicos: i) verificar o comportamento sortivo desses herbicidas frente à aplicação de biocarvões produzidos a partir de diferentes matérias-primas e T°C de pirólise, incluindo a influência de fatores como o aging dos herbicidas no solo, tamanho das partículas do biocarvão e disponibilidade de carbono orgânico dissolvido (COD) no solo promovida pela adição do biocarvão; ii) avaliar se a interação entre os herbicidas e o biocarvão afeta a eficiência de controle de braquiária (Brachiaria decumbens); iii) analisar a influência do biocarvão na dissipação e lixiviação de tebuthiuron e hexazinona; e iv) identificar o potencial de uso do biocarvão em POA, como suporte para catalisadores metálicos heterogêneos e como fonte de ferro para reações de Fenton, bem como avaliar o desempenho destes materiais na catálise oxidativa de hidrocarbonetos e dos herbicidas. Experimentos de sorção, (verificando a influência de biocarvões de diferentes matérias-primas e T°C de pirólise, aging e granulometria, além da avaliação em solos de texturas contrastantes), bem como de dissipação e lixiviação foram conduzidos, utilizando-se herbicidas radiomarcados. Em paralelo, a liberação de COD pelos biocarvões e pelos solos foi quantificada, enquanto que um experimento de eficiência de controle sobre braquiária em casa de vegetação foi conduzido. Os biocarvões foram, ainda, avaliados quanto ao potencial de uso como suporte para catalisadores metálicos e para reações de Fenton, avaliando-se sua performance para a oxidação dos herbicidas e de hidrocarbonetos. Apesar de não alterar a classe de lixiviação de tebuthiuron e hexazinona em curto prazo, quando considerado o efeito do aging, a presença de biocarvão de palha de cana-de-açúcar 550°C (PC550) no solo, independentemente da granulometria, pode auxiliar no manejo de herbicidas com elevada mobilidade, especialmente em solos de textura arenosa e com baixo teor de carbono. Neste caso, o herbicida tebuthiuron teve sua classificação alterada de \"molécula lixiviável\" (Kd,app < 5,0 L kg-1) para \"molécula não-lixiviável\" (Kd,app > 5,0 L kg-1). No entanto, o biocarvão de dejeto de galinha 350°C (DG350) aumenta o COD do solo, resultando na diminuição da sorção dos herbicidas. A adição dos biocarvões PC550 e DG350 ao solo não modificam a eficiência de controle de braquiária por moléculas altamente solúveis. Doses a partir das doses recomendadas em campo promovem controle eficiente, independentemente da presença ou não de biocarvão no solo. Tebuthiuron e hexazinona são moléculas recalcitrantes no ambiente, sendo muito baixas suas taxas de mineralização e de dissipação, tanto na presença como na ausência dos biocarvões PC550 e DG350. A presença de biocarvão no solo pouco influenciou a dissipação dessas moléculas. Os biocarvões PC550 e DG350 diminuem o potencial de lixiviação da hexazinona no solo de textura areia franca, mas não afetam o movimento vertical do tebuthiuron nas mesmas condições. Apesar do menor potencial para degradação de tebuthiuron e hexazinona em relação à epoxidação de hidrocarbonetos, a inserção do biocarvão para a síntese de catalisadores mostrou-se eficiente e permitiu o emprego deste material em processos de catálise industrial e ambiental, podendo auxiliar para o manejo da remediação de poluentes e contribuindo para expandir o uso do biocarvão. / Biochar amendments to soil has been claimed as a practice with agricultural and environmental advantages. Due to its high reactivity, biochar can interact with organic and inorganic soil contaminants, reducing the pollution potential of toxic elements and pesticides. However, pre-emergent herbicides efficacy can be negatively affected by biochar additions to the soil, which may impose higher doses and increase the environmental contamination risk. In addition, there may be increasing in the pesticide\'s persistence due to retention and lower availability of the molecules induced by biochar amendment to the soil. The interactions between biochar and the pesticides depend on the characteristics of the soil and the herbicide itself, besides the aging and the biochar\'s properties (biomass, pyrolysis T°C and granulometry). Tebuthiuron and hexazinone are herbicides with leaching potential and may have their fate modified due to the presence of biochar in the soil. These molecules have a high half-life time (t1/2) and biodegrade slowly in the environment. Thus, advanced oxidative processes (AOP) can accelerate the decomposition of herbicides and can be a way of incorporate biochar in chemical processes towards pollutants dissipation. We aimed to evaluate the effects of biochar amendments on tebuthiuron and hexazinone dynamics in soils, and the specific objectives were: i) to verify the sorption behavior of these herbicides in response to biochar\'s amendment from different feedstock and pyrolysis T°C, including the influence of factors such as herbicide aging on the soil, biochar particle size and availability of dissolved organic carbon (DOC) in the soil promoted by biochar addition; ii) to evaluate if the interaction between the herbicides and the biochars affects braquiária (Brachiaria decumbens) control efficiency; iii) to analyze the biochars influence on the dissipation and leaching of tebuthiuron and hexazinone; and iv) to identify the potential use of biochar in AOP as heterogeneous metal catalysts support and as a source of iron for Fenton reactions, as well as to evaluate the performance of these materials in oxidative catalysis of hydrocarbons and herbicides. Sorption experiments, (checking the influence of biochars from different feedstocks and pyrolysis T°C, aging and granulometry, as well as accessing the differences among soil textures), and dissipation and leaching experiments were conducted using radiolabeled herbicides. In parallel, the release of DOC by the biochars and soils was quantified, whereas an experiment in a greenhouse for braquiária control was conducted. The biochars were also evaluated for use as metal catalysts supports and for Fenton reactions, evaluating their performance for herbicides and hydrocarbons oxidation. Although it does not change tebuthiuron and hexazinone leaching class in short term, when considering the aging, the sugarcane straw biochar pyrolyzed at 550°C (PC550), regardless of granulometry, may be useful in the management of high mobility herbicides, especially in sandy soils with low carbon content. In this case, tebuthiuron had its classification modified from \"leachable\" (Kd,app < 5.0 L kg-1) for \"non-leachable\" molecule (Kd,app > 5.0 L kg-1). However, the biochar from poultry manure pyrolyzed at 350°C (DG350) increases the DOC content in the soil, resulting in decreased sorption of the herbicides. The additions of PC550 and DG350 to the soil does not modify the control efficiency of braquiária by highly soluble molecules. Doses higher than the recommended ones promote efficient control, regardless of the presence or absence of biochar in the soil. Tebuthiuron and hexazinone are highly recalcitrant molecules in the environment, having low rates of mineralization and dissipation both in the presence or absence of the biochars PC550 and DG350. The biochar application to the soil barely influenced the herbicides dissipation. The biochars PC550 and DG350 decrease the leaching potential of hexazinone in the sandy soil, but do not affect tebuthiuron leaching in the same conditions. Despite the lower potential for tebuthiuron and hexazinone degradation in relation to the epoxidation of hydrocarbons potential, biochar insertion in the synthesis of catalysts has been proved to be efficient, allowing the use of these wastes in industrial and environmental catalysis processes for pollutants remediation purposes and helping to expand the biochar range of uses.

Το στράγγισμα από τους χώρους υγειονομικής ταφής απορριμμάτων (ΧΥΤΑ) περιέχει σύνθετους οργανικούς ρύπους, με αποτέλεσμα η επεξεργασία του να έχει αποκτήσει ιδιαίτερη σημασία στις μέρες μας. Εκτός από τις μεγάλες ποσότητες οργανικού υλικού μέσα στα στραγγίσματα υπάρχουν επίσης βαρέα μέταλλα, χλωριωμένα οργανικά ή ανόργανα άλατα και γενικά διάφορες ουσίες που μπορεί να ρυπάνουν τα επιφανειακά και υπόγεια νερά. Γι ‘ αυτό κατά την κατασκευή ενός ΧΥΤΑ πρέπει να εγκατασταθούν συστήματα συλλογής και επεξεργασίας των στραγγισμάτων, ώστε να αποφευχθεί το φιλτράρισμα τους μέσω του εδάφους και τους υπεδάφους και στη συνέχεια η περαιτέρω μόλυνση ρεμάτων ή γεωτρήσεων. Στην παρούσα εργασία θα ασχοληθούμε συγκεκριμένα με τον χαρακτηρισμό των στραγγισμάτων όσον αφορά το χημικά απαιτούμενο οξυγόνο (COD), το βιοχημικά απαιτούμενο οξυγόνο (BOD), τα συνολικά αιωρούμενα στερεά (TSS) καθώς και των λοιπών φυσικοχημικών παραμέτρων τους. Επιπλέον, παρουσιάζονται κάποιες προτάσεις για την απορρύπανση των στραγγισμάτων των ΧΥΤΑ που πρέπει να γίνεται πριν από την απόρριψη τους σε οποιαδήποτε περιοχή, όπως προ-επεξεργασία των στραγγισμάτων με ένα συνδυασμό φυσικοχημικών, αναερόβιων και υδρολυτικών διαδικασιών. Για την απομάκρυνση βαρέων μετάλλων (όπως Fe, Cd, Cr) καθώς και τη μείωση του COD, μπορεί να είναι αποτελεσματική η προ-επεξεργασία με πήξη-κροκίδωση. Στην παρούσα όμως διπλωματική εργασία για τη μείωση του COD χρησιμοποιήθηκε η Φωτοκαταλυτική Διαδικασία Αποδόμησης (Photocatalytic Degradation Process), η οποία περιλαμβάνει φωτοκαταλυτική επεξεργασία με τη χρήση υπεριώδους ακτινοβολίας (UV) και την προσθήκη καταλύτη οξειδίου του τιτανίου (TiO2) στο δείγμα του στραγγίσματος. Ακόμη, εναλλακτικά χρησιμοποιήθηκε η προσρόφηση με εξανθράκωμα (biochar), Σκοπός αυτών των διαδικασιών είναι η απομάκρυνση των ανθεκτικών οργανικών ενώσεων και ο αποχρωματισμός του στραγγίσματος. Με την ολοκλήρωση των διεργασιών ο αποχρωματισμός του στραγγίσματος επιτεύχθηκε με την ετερογενή φωτοκατάλυση και η σχετική μείωση των οργανικών ρύπων με τη χρήση του ροφητικού μέσου biochar. / Leachate from landfills contains complex organic compounds, a fact that makes its effective treatment a matter of crucial importance nowadays. Apart from high quantities of organic material, leachate also contains heavy metals, organic or anorganic chloride salts and various substances which can pollute surface and ground water. As a result, the construction of landfills must include leachate collection and treatment systems, in order to prevent its filtering through ground and underground, and subsequent pollution of streams, small rivers and wells. This thesis presents the characterization of a leachate sample and testes various decontamination techniques, which could to be executed before its disposal in any area. In particular, leachate pre-treatment can be performed with a combination of physical chemical, anaerobe and hydrolytic methods. In order to remove heavy metals (i.e. Fe, Cd, Cr) and reduce COD, pre-treatment can be effective using flocculation-coagulation. In this thesis a Photocatalytic Degradation Process was used to reduce COD, which consists of photocatalytic treatment using UV radiation and adding TiO2 to the leachate sample. Alternatively, adsorption process with biochar was also tested. The purpose of this process is the removal of persistent organic compounds and the discoloration of the leachate. With the completion of the processes the discoloration of the leachate was accomplished using heterogeneous photocatalysis and the relative reduction of organic pollutes using sorption materials (i.e. biochar).

In apple (Malus domestica Borkh.) orchards, rootstock genotype, and soil fertility management practices impact soil fertility, plant associated soil microbial communities, and orchard productivity. Apple growers select rootstocks to confer beneficial traits, including size control, precocity, and pest and disease resistance. Rootstock genotype may also influence microbial communities, resulting in changes that affect tree health and productivity. Many apple growers apply synthetic nitrogen fertilizers to improve fruit yield and quality. In excess of tree requirements, nitrogen fertilizers may reduce crop yield and quality, as well as contribute to water pollution. The addition of carbon-based amendments, such as yardwaste, chicken litter composts, and biochar, may potentially reduce nitrogen and water loss, while improving soil structure and mineral nutrient availability. Orchard and pot-in-pot experiments were designed to study the following objectives: 1) determine the effects of integrated carbon-based fertilizer amendments on tree growth, productivity, and orchard soil fertility, 2) assess the effects of biochar on tree growth, leaf mineral nutrition, soil physiochemistry, and microbial community structure and activity, and 3) understand how rootstocks and fertilizers alter soil microbial communities. Applications of composts, integrated compost-calcium nitrate fertilizers, and biochar increased soil carbon, organic matter, cation exchange capacity and microbial respiration. In the orchard study, nitrogen fertilizer application did not increase tree growth, fruit quality, or leaf nitrogen concentration. Biochar applied at high rates with nitrogen fertigation increased tree growth and leaf nitrogen concentration similar to nitrogen fertigation. In the pot-in-pot compost study, chicken litter compost increased tree growth, and integrated compost-calcium nitrate fertilizer applications increased leaf N concentration. Analysis of the microbial community structure of bulk soil samples from the biochar and compost pot-in-pot experiments determined that the community structure was similar for all treatments during the three-year study. Metagenomic sequencing of the rhizosphere bacterial community indicated that compost applications altered community diversity and evenness, and that compost treatments were more similar to each other than to the calcium nitrate treatment. Data from my dissertation research suggests that compost can be used to increase orchard soil fertility, tree growth, and leaf nutrition, and that compost applications increase soil microbial community diversity and activity. / Ph. D.