Hazelnuts are mostly non-dormant at harvest but develop seed dormancy after a few days of storage. The seeds have been classified as recalcitrant since they cannot be stored for more than one year under ambient conditions. Cryopreservation has not been satisfactory so an alternative protocol is required. To test for recalcitrance, chilled non-dormant seeds (control) were compared with gibberellic acid (GA3) treated seeds during 6 weeks storage at 5°C or at ambient temperature. Control seed moisture content (MC) was 14-15% compared with 20% for GA3 treated seeds. No change in viability was noted until the end of 6 weeks at ambient temperature, when infection proliferated. Reduced germinability, associated with increased leachate conductivity, was noted on all treatments and controls, with ambient temperature storage most harmful for seed viability. This supports classification of hazel seeds as recalcitrant. However, orthodox behaviour could be induced by reducing seed moisture to <6%, showing survival for more than 3 years at -20°C with acceptable germinability and producing healthy seedlings. Pathogen tests show that 6 weeks chilling to break seed dormancy may activate the seeds’ internal protective mechanisms, thereby reducing infection and enabling germination and healthy seedling establishment. The link between seed viability and protection from free radicals and pathogens was examined. Antioxidant activity in hazelnut seed associates (such as endocarp, funiculus and testa) was found to be much higher than in the seed embryo, perhaps indicating that hazel seeds have natural protective mechanisms within the pericarp. Antioxidant activity of seed associates increased during chilling, indicating their role in protecting the seed. Nevertheless, TTC test revealed that seeds acclimatised to ii < 6% MC and stored at 5°C for 45 weeks showed viability loss due to damage of the embryonic axes, probably caused by free radicals. Initial tests to stabilise seed moisture content showed that reduction in seed moisture did not impose dormancy and seed moisture content (MC) stabilisation resulted in > 80% germination but many abnormal seedlings. Dormancy reversibility was tested by treatments T1 (one period at 15°C) and T2 (two periods at 15°C), designed following a consideration of the natural environment. Both resulted in reduced germination, delayed seedling emergence, increased abnormal seedlings, reduced seedling height and decreased internode numbers. To test the role of temperature in reduced seed performance, non-dormant hazelnuts were held at either 5°C or at ambient temperature for up to 6 weeks. Seeds from both sets exhibited high viability, but germinability was significantly decreased in the ambient temperature set, associated with increases in leachate conductivity and infection. Work in this thesis has confirmed that dormancy was broken by chilling, with gradually increasing germination as chilling time was increased. Germination increased with increase in chilling and reduction in infection. No infection was recoreded after 6 weeks chilling. It is most likely that protective agents are produced causing suppression of infection. In these experiments it was observed that not all germinated seeds produced healthy seedlings, suggesting that germination tests without observation of seedlings may give an incomplete assessment of germination success. Assessment using the Tetrazolium test (TTC) was found to be much more dependable and it was also possible to detect damage to specific tissues that might result in unhealthy seedlings.

Biomass recalcitrance has been recognized as one of the major barriers that hided the cost-effective conversion of lignocellulosic biomass to bioethanol, therefore the current bioconversion process require an essential step known as pretreatment to increase the cellulose accessibility. This thesis provides information about changes in cellulose accessibility upon different pretreatments, along with how these pretreatments alter the chemical and physical structures of biomass, will be extremely helpful to further optimize the current pretreatment process. Multiple promising analytical techniques including Simons’ stain, NMR cryoporometry, relaxometry, mercury porosimetry was introduced and successfully applied on pretreated biomass samples to characterize the cellulose accessible surface area and biomass porosity. Different pretreatments increase cellulose accessibility through different mechanisms to different extent. Dilute acid pretreatment is more effective than steam explosion in terms of increasing accessible surface area of cellulose as reflected by Simons’ stain and NMR cryoporometry, while NMR relaxometry suggested steam explosion is more effective at pore expansion for the cell wall water pools detected by changes in NMR relaxation time. Alkaline pretreatment decreased cellulose degree of polymerization, cellulose crystallinity, lignin content and subsequently increased cellulose accessibility, with sodium hydroxide pretreatment proved to be much more effective compared lime or soaking in ammonia pretreatment. Delignification through alkaline-based pretreatment is found less effective than removal of hemicellulose using acid in terms of cellulose accessibility increase. Lignin didn’t directly dictate cellulose accessibility but rather restricted xylan accessibility which in turn controls the access of cellulase to cellulose. Pore size distribution analysis based on mercury porosimetry also indicated that the most fundamental barrier in terms of biomass porosity scale for efficient enzymatic hydrolysis is the nano-pore space formed between coated microfibrils, despite some of the porous architecture such as cell lumen and pit could be severely destroyed after pretreatment. The action of cellulase on the characteristics of cellulosic fractions obtained from pretreated biomass was also investigated. Cellulose accessibility was found to increase at the beginning of hydrolysis, and after reaching a maximum value then starting to decrease. Enzymatic hydrolysis resulted in a rapid decrease in the cellulose degree of polymerization then gradually leveled off, suggesting the existence of a synergistic action of endo- and exo-glucanases that contribute to the occurrence of a peeling off type mechanism.

The work of the present thesis focused on conversion of the cellulosic part of waste textiles into biogas and ethanol, and its challenges. In 2009, the global annual fiber consumption exceeded 70 Mt, of which around 40% consisted of cellulosic material. This huge amount of fibers is processed into apparel, home textiles, and industrial products, ending up as waste after a certain time delay. Regretfully, current management of waste textiles mainly comprises incineration and landfilling, in spite of the potential of cellulosic material being used in the production of ethanol or methane. The volume of cellulose mentioned above would be sufficient for producing around 20 billion liters of ethanol or 11.6 billion Nm3 of methane per year. Nevertheless, waste textiles are not yet accepted as a suitable substrate for biofuel production, since their processing to biofuel presents certain challenges, e.g. high crystallinity of cotton cellulose, presence of dyes, reagents and other materials, and being textiles as a mixture of natural and synthetic fibers. High crystallinity of cotton cellulose curbs high efficient conversion by enzymatic or bacterial hydrolysis, and the presence of non-cellulosic fibers may create several processing problems. The work of the present thesis centered on these challenges. Cotton linter and blue jeans waste textiles, all practically pure cellulose, were converted to ethanol by SSSF, using S. cerevisiae, with a yield of about 0.14 g ethanol/g textile, only 25% of the theoretical yield. To improve the yield, a pretreatment process was required and thus, several methods were examined. Alkaline pretreatments significantly improved the yield of hydrolysis and subsequent ethanol production, the most effective condition being treatment with a 12% NaOH-solution at 0 °C, increasing the yield to 0.48 g ethanol/g textile (85% of the theoretical yield). Waste textile streams, however, are mixtures of different fibers, and a separation of the cellulosic fibers from synthetic fibers is thus necessary. The separation was not achieved using an alkaline pretreatment, and hence another approach was investigated, viz. pretreatment with N-methyl-morpholine-N-oxide (NMMO), an industrially available and environment friendly cellulose solvent. The dissolution process was performed under different conditions in terms of solvent concentration, temperature, and duration. Pretreatment with 85% NMMO at 120 °C under atmospheric pressure for 2.5 hours, improved the ethanol yield by 150%, compared to the yield of untreated cellulose. This pretreatment proved to be of major advantage, as it provided a method for dissolving and then recovering the cellulose. Using this method as a foundation, a novel process was developed, refined and verified, by testing polyester/cellulose-blended textiles, which predominate waste textiles. The polyesters were purified as fibers after the NMMO treatments, and up to 95% of the cellulose content was regenerated. The solvent was then recovered, recycled, and reused. Furthermore, investigating the effect of this treatment on anaerobic digestion of cellulose disclosed a remarkable enhancement of the microbial solubilization; the rate in pretreated textiles was twice the rate in untreated material. The overall yield of methane was, however, not significantly affected. The process developed in the present thesis appears promising for transformation of waste textiles into a suitable raw material, to subsequently be used for biological conversion to ethanol and biogas. / <p>Thesis to be defended in public on Friday, May 27, 2011 at 13.00 at KC-salen, Kemigården 4, Göteborg, for the degree of Doctor of Philosophy.</p>

Este estudo avaliou a ocorrência e as características da hemicelulose em gramíneas e sua correlação com a recalcitrância da biomassa lignocelulósica frente à digestão enzimática. As amostras de gramíneas incluíram seis híbridos de cana-de-açúcar com teores variados de lignina e hemicelulose, além de uma variedade de sorgo forrageiro. Os entrenós de cana-de-açúcar madura foram fracionados em três regiões distintas: medula, interface medula-córtex e córtex. O sorgo foi fracionado em: medula e córtex. As medulas apresentaram alto teor de glucanas (40-55%) e baixo teor de ligninas (14-22%). O teor de xilanas aumentou da medula (14-20%) para o córtex (20-23%). A composição da hemicelulose também foi avaliada. Xilose (9- 23%), glicose (1-12%) e arabinose (1-4%) foram os monômeros mais abundantes ao fim das análises. As medulas apresentaram xilanas mais arabinosiladas e alta deposição de glucanas não celulósicas. O teor de (1 ? 3),(1 ? 4)-ß-D-glucanas foi elevado nas medulas (1,4-15%) e diminuiu no sentido do córtex (0,1 - 1%). As arabinoxilanas de cana-de-açúcar foram submetidas à um estudo estrutural, confirmando que as cadeias de xilanas são substituídas. A lignina foi avaliada por pirólise acoplada com espectrometria de massas, revelando uma estrutura HGS em cana-de-açúcar e uma razão S/G sem um padrão progressivo entre as frações do entrenó. As amostras de cana-de-açúcar também foram avaliadas quanto à distribuição de hemiceluloses entre os diferentes tecidos e células através de microscopia de imunofluorescência. Uma análise preliminar revelou que anticorpos específicos para xilana e (1 ? 3),(1 ? 4)-ß-D-glucana se ligaram aos extratos hemicelulósicos. Cortes das amostras foram tratados com os anticorpos CRCC-M140 e LM11 (para xilanas menos e mais substituídas) e outro contra (1 ? 3),(1 ? 4)-ß-Dglucanas. Epítopos de xilanas menos substituídas estiveram presentes principalmente em feixes vasculares e não foram detectados em parênquima de medulas. Epítopos de arabinoxilana foram encontrados em todas as frações e tipos celulares. A imunofluorescência de (1-->3),(1-->4)-ß-D-glucanas mostrou que estes estão depositados principalmente em células do parênquima de medulas; em feixes vasculares estes foram detectados apenas em células do floema e protoxilema. O índice de cristalinidade foi estimado para as amostras. Altos índices de cristalinidade foram encontrados para amostras do córtex (0,44-0,56). As amostras (sem prétratamentos) foram digeridas com enzimas celulolíticas comerciais. As medulas foram hidrolisadas mais facilmente (32-85% de conversão de glucanas após 72h), enquanto amostras do córtex foram mais recalcitrantes (2-9%). As interfaces apresentaram conversões intermediárias (7-46%). A hidrólise da xilana ocorreu em menor escala para todas frações, possivelmente devido ao alto grau de substituição das xilanas. A digestibilidade das glucanas foi diretamente proporcional ao grau de substituição das xilanas (R2=0,86) e ao teor de (1-->3),(1-->4)-ß-D-glucanas nas amostras (R2 = 0,92). Entre as amostras de gramíneas, aqueles que apresentam menor recalcitrância reuniram características que incluem baixo teor de lignina, alto teor de (1-->3),(1-->4)- ß-D-glucanas e alto grau de substituição das xilanas. Essas características poderiam ser utilizadas como indicadores nos processos de geração e seleção de plantas para a produção de biomassas lignocelulósicas de elevada digestibilidade. / This work assessed the occurrence and features of hemicellulose in grasses as related to lignocellulosic biomass recalcitrance to enzymatic hydrolysis. The grasses materials included six sugarcane hybrids with varying lignin and hemicellulose content, besides a variety of forage sorghum. The mature sugarcane internodes were dissected into three different regions: pith, pith-rind interface and rind. The sorghum was dissected into pith and rind. Pith samples presented high glucan content (40- 55%) and low lignin content (14-22%). The xylan content increased from pith region (14-20%) to rind (20-23%). Hemicellulose composition was also assessed. Xylose (9- 23%), glucose (1-12%) and arabinose (1-4%) were the most abundant monomers at the end of the analyzes. Pith samples had the most arabinosilated xylans and high content of non-cellulosic glucans. The (1-->3),(1-->4)-ß-D-glucan content was high in piths (1,4-15%) and decreased towards rind (0,1-1%). The sugarcane arabinoxylans were submitted to a study of their structure, which confirmed the xylan backbone was substituted. Lignin was assessed by pyrolysis coupled with mass spectrometer, which showed an HGS polymer in sugarcane and a S/G ratio without a progressive pattern between internode fractions. The sugarcane samples were also evaluated as related to hemicellulose distribution between different tissues and cells by immunofluorescence microscopy. A preliminary analysis showed that antibodies specific to xylan and mixed-linkage glucan bound to hemicellulose extracts. Plant sections were treated with the antibodies CRCC-M140 and LM11 (for less and more substituted xylans) and another one against mixed-linkage glucans. Less decorated xylan epitopes were mainly present in vascular bundles and were not detected in pith parenchyma. Arabinoxylan epitopes were found in all fractions and cell types. The mixed-linkage glucan immunofluorescence showed they were mainly deposited in parenchyma cells from piths; they were only detected in phloem and protoxylem cells in vascular bundles. The crystallinity index was estimated for all samples. High crystallinity indexes were found in rind samples (0,44-0,56). The non-pretreated materials were digested with commercial cellulolytic enzymes. Piths were easily hydrolyzed (32-85% of glucan conversion after 72h), while rind samples were more recalcitrant (2-9%). Interface samples showed intermediary conversions (7-46%). Xylan hydrolysis occurred in a less extent for all fractions, possibly due to a high substitution level on xylans. The glucan digestibility was proportionally related to the substitution level of xylan (R2=0,86) and the mixed-linkage glucan content (R2 = 0,92). Among the grasses samples, those with lower recalcitrance had features such as low lignin content, high mixed-linkage glucan content and high substitution level of xylans. These features could serve as indicators in the process of generation and selection of plants for lignocellulosic biomass production with high digestibility degree.

Este estudo avaliou a ocorrência e as características da hemicelulose em gramíneas e sua correlação com a recalcitrância da biomassa lignocelulósica frente à digestão enzimática. As amostras de gramíneas incluíram seis híbridos de cana-de-açúcar com teores variados de lignina e hemicelulose, além de uma variedade de sorgo forrageiro. Os entrenós de cana-de-açúcar madura foram fracionados em três regiões distintas: medula, interface medula-córtex e córtex. O sorgo foi fracionado em: medula e córtex. As medulas apresentaram alto teor de glucanas (40-55%) e baixo teor de ligninas (14-22%). O teor de xilanas aumentou da medula (14-20%) para o córtex (20-23%). A composição da hemicelulose também foi avaliada. Xilose (9- 23%), glicose (1-12%) e arabinose (1-4%) foram os monômeros mais abundantes ao fim das análises. As medulas apresentaram xilanas mais arabinosiladas e alta deposição de glucanas não celulósicas. O teor de (1 ? 3),(1 ? 4)-ß-D-glucanas foi elevado nas medulas (1,4-15%) e diminuiu no sentido do córtex (0,1 - 1%). As arabinoxilanas de cana-de-açúcar foram submetidas à um estudo estrutural, confirmando que as cadeias de xilanas são substituídas. A lignina foi avaliada por pirólise acoplada com espectrometria de massas, revelando uma estrutura HGS em cana-de-açúcar e uma razão S/G sem um padrão progressivo entre as frações do entrenó. As amostras de cana-de-açúcar também foram avaliadas quanto à distribuição de hemiceluloses entre os diferentes tecidos e células através de microscopia de imunofluorescência. Uma análise preliminar revelou que anticorpos específicos para xilana e (1 ? 3),(1 ? 4)-ß-D-glucana se ligaram aos extratos hemicelulósicos. Cortes das amostras foram tratados com os anticorpos CRCC-M140 e LM11 (para xilanas menos e mais substituídas) e outro contra (1 ? 3),(1 ? 4)-ß-Dglucanas. Epítopos de xilanas menos substituídas estiveram presentes principalmente em feixes vasculares e não foram detectados em parênquima de medulas. Epítopos de arabinoxilana foram encontrados em todas as frações e tipos celulares. A imunofluorescência de (1-->3),(1-->4)-ß-D-glucanas mostrou que estes estão depositados principalmente em células do parênquima de medulas; em feixes vasculares estes foram detectados apenas em células do floema e protoxilema. O índice de cristalinidade foi estimado para as amostras. Altos índices de cristalinidade foram encontrados para amostras do córtex (0,44-0,56). As amostras (sem prétratamentos) foram digeridas com enzimas celulolíticas comerciais. As medulas foram hidrolisadas mais facilmente (32-85% de conversão de glucanas após 72h), enquanto amostras do córtex foram mais recalcitrantes (2-9%). As interfaces apresentaram conversões intermediárias (7-46%). A hidrólise da xilana ocorreu em menor escala para todas frações, possivelmente devido ao alto grau de substituição das xilanas. A digestibilidade das glucanas foi diretamente proporcional ao grau de substituição das xilanas (R2=0,86) e ao teor de (1-->3),(1-->4)-ß-D-glucanas nas amostras (R2 = 0,92). Entre as amostras de gramíneas, aqueles que apresentam menor recalcitrância reuniram características que incluem baixo teor de lignina, alto teor de (1-->3),(1-->4)- ß-D-glucanas e alto grau de substituição das xilanas. Essas características poderiam ser utilizadas como indicadores nos processos de geração e seleção de plantas para a produção de biomassas lignocelulósicas de elevada digestibilidade. / This work assessed the occurrence and features of hemicellulose in grasses as related to lignocellulosic biomass recalcitrance to enzymatic hydrolysis. The grasses materials included six sugarcane hybrids with varying lignin and hemicellulose content, besides a variety of forage sorghum. The mature sugarcane internodes were dissected into three different regions: pith, pith-rind interface and rind. The sorghum was dissected into pith and rind. Pith samples presented high glucan content (40- 55%) and low lignin content (14-22%). The xylan content increased from pith region (14-20%) to rind (20-23%). Hemicellulose composition was also assessed. Xylose (9- 23%), glucose (1-12%) and arabinose (1-4%) were the most abundant monomers at the end of the analyzes. Pith samples had the most arabinosilated xylans and high content of non-cellulosic glucans. The (1-->3),(1-->4)-ß-D-glucan content was high in piths (1,4-15%) and decreased towards rind (0,1-1%). The sugarcane arabinoxylans were submitted to a study of their structure, which confirmed the xylan backbone was substituted. Lignin was assessed by pyrolysis coupled with mass spectrometer, which showed an HGS polymer in sugarcane and a S/G ratio without a progressive pattern between internode fractions. The sugarcane samples were also evaluated as related to hemicellulose distribution between different tissues and cells by immunofluorescence microscopy. A preliminary analysis showed that antibodies specific to xylan and mixed-linkage glucan bound to hemicellulose extracts. Plant sections were treated with the antibodies CRCC-M140 and LM11 (for less and more substituted xylans) and another one against mixed-linkage glucans. Less decorated xylan epitopes were mainly present in vascular bundles and were not detected in pith parenchyma. Arabinoxylan epitopes were found in all fractions and cell types. The mixed-linkage glucan immunofluorescence showed they were mainly deposited in parenchyma cells from piths; they were only detected in phloem and protoxylem cells in vascular bundles. The crystallinity index was estimated for all samples. High crystallinity indexes were found in rind samples (0,44-0,56). The non-pretreated materials were digested with commercial cellulolytic enzymes. Piths were easily hydrolyzed (32-85% of glucan conversion after 72h), while rind samples were more recalcitrant (2-9%). Interface samples showed intermediary conversions (7-46%). Xylan hydrolysis occurred in a less extent for all fractions, possibly due to a high substitution level on xylans. The glucan digestibility was proportionally related to the substitution level of xylan (R2=0,86) and the mixed-linkage glucan content (R2 = 0,92). Among the grasses samples, those with lower recalcitrance had features such as low lignin content, high mixed-linkage glucan content and high substitution level of xylans. These features could serve as indicators in the process of generation and selection of plants for lignocellulosic biomass production with high digestibility degree.

Despite the importance of soil organic matter (SOM) in C storage and provision of ecosystem services, the magnitude and direction of the response of SOM to climate change remains debated. Particularly contested is the role of biochemical recalcitrance in determining the biological stability of SOM, which in turn, may also vary with climate. Employing a climosequence study design controlling for confounding pedogenic factors, the research described in this thesis aimed to uncover the response of both SOM chemistry and SOM biological stability to changes in climate and associated land use shifts at the grassland-forest ecotone in west-central Saskatchewan. Characterization of SOM chemistry was achieved using two advanced analytical techniques: X-ray absorption near edge structure (XANES) spectroscopy and pyrolysis-field ionization mass spectrometry (Py-FIMS). Agreements between XANES and Py-FIMS revealed only minor differences in SOM chemistry resulting from a 0.7 °C mean annual temperature (MAT) gradient and associated broad differences in land use, but revealed a clear influence of depth within soil profiles. In contrast, long-term aerobic incubations revealed that biological stability of SOM varied with both climate and climate-induced differences in land use, but was not largely influenced by depth. Together, these findings suggest a decoupling of SOM chemistry and its biological stability, indicating that factors other than biochemical recalcitrance are the primary drivers of SOM persistence in these soils.

Financiadora de Estudos e Projetos / Um dos grandes problemas enfrentados no tratamento de lixiviado é a definição de suas características físico-químicas e biológicas. Neste contexto, o objetivo do presente trabalho é avaliar a composição química, a recalcitrância, e a toxicidade do lixiviado bruto e tratado por processos de tratamento (físico-químico e biológico) oriundo do Aterro Metropolitano de Gramacho, localizado no município de Duque de Caxias, no estado do Rio de Janeiro. Os resultados mostraram maior biodegradabilidade aeróbia no efluente físico-químico com percentuais variando de 7% a 35 %. A natureza de tais compostos justifica a natureza refratária do lixiviado e alerta pela toxicidade que podem atribuir tanto aos microrganismos envolvidos no processo quanto a saúde humana quando dispostos incorretamente. Para o lixiviado em estudo, observou-se a diminuição da toxicidade ao passar pelo processo físicoquímico. Dessa maneira, observou-se que é necessário a adoção de sistemas de tratamento que conjuguem processos físico-químicos atuando como pré ou pós-tratamento de processos biológicos. Sendo assim, os resultados obtidos mostram a importância deste tipo de caracterização, como fonte de subsídios para a seleção, projeto e avaliação de sistemas de tratamento. / Leachate from Municipal Solid Waste are characterized by high concentration of refractory organic matter, ammonia and toxic compounds. In this context, the objective of this study is to evaluate the chemical composition, the recalcitrance and toxicity of raw and treated leachate for treatment processes (physical and biological) from the Gramacho Metropolitan Landfill, located in the municipality of Duque de Caxias, in the state of Rio de Janeiro. The results showed higher aerobic biodegradability in the effluent physicochemical with percentages ranging from 7% to 35%. The nature of some compounds justifies the refractory nature of the leachate and alert the toxicity that can assign both the microorganisms involved in the process as human health when disposed improperly. Thus, it was observed that it is necessary to adopt treatment systems that combine physical and chemical processes acting as a propost treatment of biological processes. Thus, the results show the importance of this type of characterization, as a source of information for the selection, design and evaluation of treatment systems.

Financiadora de Estudos e Projetos / Um dos grandes problemas enfrentados no tratamento de lixiviado é a definição de suas características físico-químicas e biológicas. Neste contexto, o objetivo do presente trabalho é avaliar a composição química, a recalcitrância, e a toxicidade do lixiviado bruto e tratado por processos de tratamento (físico-químico e biológico) oriundo do Aterro Metropolitano de Gramacho, localizado no município de Duque de Caxias, no estado do Rio de Janeiro. Os resultados mostraram maior biodegradabilidade aeróbia no efluente físico-químico com percentuais variando de 7% a 35 %. A natureza de tais compostos justifica a natureza refratária do lixiviado e alerta pela toxicidade que podem atribuir tanto aos microrganismos envolvidos no processo quanto a saúde humana quando dispostos incorretamente. Para o lixiviado em estudo, observou-se a diminuição da toxicidade ao passar pelo processo físicoquímico. Dessa maneira, observou-se que é necessário a adoção de sistemas de tratamento que conjuguem processos físico-químicos atuando como pré ou pós-tratamento de processos biológicos. Sendo assim, os resultados obtidos mostram a importância deste tipo de caracterização, como fonte de subsídios para a seleção, projeto e avaliação de sistemas de tratamento. / Leachate from Municipal Solid Waste are characterized by high concentration of refractory organic matter, ammonia and toxic compounds. In this context, the objective of this study is to evaluate the chemical composition, the recalcitrance and toxicity of raw and treated leachate for treatment processes (physical and biological) from the Gramacho Metropolitan Landfill, located in the municipality of Duque de Caxias, in the state of Rio de Janeiro. The results showed higher aerobic biodegradability in the effluent physicochemical with percentages ranging from 7% to 35%. The nature of some compounds justifies the refractory nature of the leachate and alert the toxicity that can assign both the microorganisms involved in the process as human health when disposed improperly. Thus, it was observed that it is necessary to adopt treatment systems that combine physical and chemical processes acting as a propost treatment of biological processes. Thus, the results show the importance of this type of characterization, as a source of information for the selection, design and evaluation of treatment systems.

Submitted by Viviane Lima da Cunha (viviane@biblioteca.ufpb.br) on 2017-07-20T14:17:33Z No. of bitstreams: 1 arquivototal.pdf: 2910252 bytes, checksum: acd75eea8212603d7149d077ca346e9b (MD5) / Made available in DSpace on 2017-07-20T14:17:33Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2910252 bytes, checksum: acd75eea8212603d7149d077ca346e9b (MD5) Previous issue date: 2016-03-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The solar photo-Fenton process appears as an attractive alternative to post-treatment of landfill leachate to reduce the recalcitrant organic load of these effluents and, at the same time, to reduce energy costs of treatment by the use of a clean, renewable and free energy source. In this way, the present study aimed to evaluate the efficiency of the solar photo- Fenton process in the final physicochemical and toxicological quality of the biologically pretreated leachate from the landfill of João Pessoa city using a pilot-scale photoreactor. Initially, the operating conditions were investigated (flow, reaction time and pH adjustment) for the solar photo-Fenton process in pilot-scale. For this, three tests were performed with different flow rates (test1=65L.min-1, test2 = 48L.min-1, test3 = 35L.min-1). Then, the test 4 was carried to evaluate the reaction time process (60, 120 and 180 minutes) and the influence of pH adjustment (pH8) in the samples after the process. Under defined conditions, the efficiency of the solar photo-Fenton process was evaluated in terms of physicochemical and toxicological parameters (test 5). The influence of solar photolysis treatment was also observed. As a result, it was verified that the flow does not interfere directly in the removal of COD; then the minimum flow (35L.min-1) was adopted. In 60 minutes of reaction, it was possible to obtain high COD (76.1%) and color (93.45%) removals, so, this time was chosen for the process. The pH adjustment procedure was adopted to standardize the phototreated samples, since it increased the COD removal around 4%. In general, there was no change in the physicochemical characteristics of the leachate after the solar photolysis process. The solar photo-Fenton process provided high removals of color (87.5%), COD (81.7%) and recalcitrance, in terms of BOD5/COD (which increased from 0.12 to 0.32) and aromatic compounds (A254: 87,1% and A280: 87,74%). In addition, the solar photo-Fenton process reduced 76% of the leachate phytotoxicity on the lettuce plant (Lactuca sativa), in terms of EC50. In that way, it can be concluded that the solar photo-Fenton process was efficient when applied in pilot-scale, acting as an interesting post-treatment alternative for reduction of COD, color, recalcitrance and toxicity from landfill leachate. / O processo foto-Fenton solar surge como uma alternativa atrativa no pós-tratamento de lixiviados de aterros sanitários capaz de atuar na redução da carga orgânica recalcitrante desses efluentes e, ao mesmo tempo, possibilitar a miminização dos custos energéticos do tratamento pela utilização de uma fonte limpa, renovável e gratuita de energia. Dessa forma, a presente pesquisa objetivou avaliar a eficiência do processo foto-Fenton solar na qualidade físico-química e toxicológica final do lixiviado proveniente do sistema de tratamento biológico do Aterro Sanitário Metropolitano de João Pessoa (ASMJP) usando um fotorreator em escala piloto. Inicialmente, foram investigadas as condições operacionais (vazão, tempo de reação e ajuste do pH) para o processo foto-Fenton solar, em escala piloto. Para isso, foram realizados três testes com vazões diferenciadas (teste1=65L.min-1; teste2=48L.min-1; teste3=35L.min-1). Foi realizado ainda o teste 4, onde o tempo de reação (60, 120 e 180 minutos) foi investigado, bem como verificou-se a influência do ajuste de pH (pH8) nas amostras após o tratamento. Sob as condições definidas, a eficiência do processo foto-Fenton solar foi avaliada em termos de parâmetros físicos, químicos e toxicológicos (teste 5). A influência da fotólise solar no tratamento também foi verificada. Como resultados, pôde-se observar que a vazão não interferiu diretamente na remoção de DQO das amostras, adotou-se então a vazão mínima estudada (35L.min-1). Observou-se ainda que em 60 minutos de reação já foi possível obter elevados percentuais de remoção de DQO (76,1%) e cor (93,45%), sendo portanto o tempo escolhido para o tratamento. O procedimento de ajuste de pH foi adotado para padronização das amostras fototratadas, visto que ele elevou a remoção de DQO em torno de 4%. Em geral, não se verificou alteração nas características físico-químicas do lixiviado após a fotólise solar. O processo foto-Fenton solar proporcionou elevadas eficiências de remoção de cor (87,5%), DQO (81,7%) e recalcitrância, em termos de DBO5/DQO (que aumentou de 0,12 para 0,32) e redução de compostos aromáticos (A254: 87,1% e A280: 87,74%). Além de que, reduziu em 76% a elevada fitotoxicidade do lixiviado sobre a espécie Lactuca sativa (alface), em termos de CE50. Assim, pode-se concluir que o processo foto- Fenton solar foi eficiente quando aplicado em escala piloto sendo uma alternativa de póstratamento interessante na redução de DQO, cor, recalcitrância e toxicidade do lixiviado.

Introdução sistemas de tratamento de esgotos, quando aplicados ao tratamento de lixiviado de aterro sanitário, não têm apresentado bons resultados. Por conta disso, faz-se necessário o desenvolvimento de alternativas para o tratamento de lixiviado. Objetivo avaliar o pós-tratamento de lixiviado de aterro sanitário por wetland construído de fluxo subsuperficial horizontal e reator biológico de leito móvel (RBLM). Materiais e métodos foram realizados dois experimentos com tratamento de lixiviado após remoção de amônia por dessorção. No experimento 1 utilizou-se wetlands construídos de fluxo horizontal em escala de bancada (volume total de 30,8 L), plantados com Cyperus papyrus, Heliconia psittacorum e Gynerium sagittatum, e um controle sem vegetação, preenchidos com pedrisco calcário. O sistema foi alimentado com lixiviado diluído em água em diferentes proporções (entre 10 por cento e 30 por cento ) com concentração média de DQO entre 336 e 750 mg.L-1 e nitrogênio amoniacal (N-NH4) entre 47 e 199 mg.L-1. A operação ocorreu em três etapas: (1ª) alimentação contínua e TDH médio entre 2,7 e 5,3 d; (2ª) regime de ciclos de recirculação do efluente, para avaliar o efeito do aumento de TDH para 21 dias; (3ª) alimentação contínua de duas unidades wetlands em série, visando elevar o TDH (entre 8,1 e 9,9 d) sem recirculação. O experimento 2 foi implantado em escala piloto, com uma unidade de dessorção de amônia seguida de um Reator Biológico de Leito Móvel (RBLM) e um biofiltro anóxico. O RBLM (volume efetivo de 380 L) foi preenchido em 50 por cento com anel pall. Resultados e discussão No experimento 1, obteve-se baixa remoção de DQO com médias inferiores a 40 por cento e concentração final entre 270 e 750 mg.L-1. No entanto, verificou-se remoção de N-NH4, principalmente na 2ª e 3ª etapas, com médias de remoção entre 43 por cento e 81 por cento , resultando em concentração de 20 a 223 mg.L-1, com influência do TDH. No experimento 2, problemas técnicos durante a instalação e operação inicial e interdição do campus da USP-Leste prejudicaram a adaptação do reator e impediram o seu monitoramento por tempo suficiente para geração de dados consistentes, sendo interrompido na fase inicial. Conclusões A baixa eficiência para DQO provavelmente está relacionada à recalcitrância do lixiviado, ou devido à inibição dos microrganismos por toxicidade. Quanto ao N-NH4, infere-se que o aumento do TDH proporcionou maior tempo de difusão de oxigênio para o sistema wetland, suprindo a demanda das bactérias heterotróficas, o que possibilitou utilização do oxigênio excedente pelas nitrificantes, culminando na oxidação do N-NH4. / Introduction sewage treatment systems, when applied to the treatment of landfill leachate, have not shown good results. Thus it is necessary to develop alternatives for the treatment of leachate. Objective To assess the post-treatment of landfill leachate by horizontal subsurface flow constructed wetland and moving bed biofilm reactor (MBBR). Materials and methods Two experiments were conducted with treatment of the leachate after removal of ammonia by stripping. In experiment 1, horizontal flow constructed wetlands, at bench scale (total volume of 30.8 L), planted with Cyperus papyrus, Heliconia psittacorum and Gynerium sagittatum, and a control without vegetation, were filled with calcareous gravel. The system was fed with leachate diluted in water with different proportions (between 10 per cent and 30 per cent ) with mean COD concentration of between 336 and 750 mg.L-1 and ammonia nitrogen (NH4-N) between 47 and 199 mg L-1. The operation was divided in three stages: (1st) continuous feeding with mean HRT between 2.7 and 5.3 d; (2nd) regime of effluent recirculation to evaluate the effect of increasing the HRT to 21 days; (3rd) continuous feeding with two wetlands units in series, aimed HRT increasing (between 8.1 and 9.9 d) without recirculation. Experiment 2 was implemented on a pilot scale, with a unit of ammonia stripping followed by MBBR and an anoxic biofilter. The MBBR (380 L working volume) was filled 50 per cent with pall ring. Results and discussion In experiment 1, the COD removal was low, with averages below 40 per cent , with effluent concentration between 270 and 750 mg.L-1. However, there was removal of NH4-N, especially in the 2nd and 3rd stages, with average removal between 43 per cent and 81 per cent , resulting in concentration between 20 and 223 mg.L-1, with HRT influence. In experiment 2, technical problems during the installation and initial operation and interdiction of the campus of USP-Leste disrupted the reactor acclimation and precluded the monitoring for sufficient time to generate consistent data for discussion. Conclusions The low efficiency for COD is probably related to the recalcitrance of the leachate, or due to inhibition of microorganisms by toxicity. For NH4-N, it is inferred that the increase of the HRT provided greater time for diffusion of oxygen to the wetland system, meeting the demand of heterotrophic bacteria, which allowed the use of excess oxygen by nitrifiers, culminating in the oxidation of NH4-N.