Sustainable and environmentally friendly waste-to-energy conversion technologies, such as anaerobic digestion (AD) and gasification, have received significant attention in recent energy research. These technologies have proven their ability to reduce reliance on fossil fuels and greenhouse gas emissions by converting organic waste into products and fuels with market value, such as biomass, biogas, and synthetic gas. Since the syngas produced by biomass gasification contains highly toxic CO and flammable H₂, converting syngas into renewable natural gas has recently gained a lot of interest. By coupling AD with syngas, microbial consortium in the AD reactor converts the syngas into methane through a process known as biomethanation. Feeding syngas into the AD reactor is a method that not only can enhance methane production by conversion of CO₂ to CH₄ during the AD process but also converts syngas into methane as pure energy. This study aims to assess and compare the effect of different syngas compositions on methane production and optimize the SB process by identifying the best syngas composition and gas-biomass ratio under mesophilic temperature conditions. The study was conducted using batch and semi-continuous reactors in a lab-scale setting. The results of this study can contribute to the development of more efficient and sustainable methods for SB. In phase I of this study, syngas biomethanation under different syngas compositions was conducted under three different gas-biomass ratios (0.5, 1 and 1.5) in bench-scale experiments to study the impact on CO and H₂ partial pressure and CO toxicity on operation parameters (e.g., pH and VFA) and syngas conversion efficiency. The results showed that the optimum syngas composition with the highest amount of CH₄ is H₂-rich syngas (CO₂:CO; H₂ 1:1:7) and syngas with stoichiometric ratios between H₂ and CO/CO₂ (CO:H₂ 1:3; CO₂:H₂ 1:4) because of the sufficient available amount of hydrogen in the headspace. Methane content in the produced biogas reached 80.0%, 63.6% and 57.7%, respectively, compared to the control sample with 30.2% methane in the headspace. In phase II, the optimum syngas compositions were selected for experimenting with semi-continuous mode to 1) investigate the effect of injecting syngas in several stages in increasing syngas conversion efficiency, 2) adapt microorganisms to hydrogen and enhance biohydrogen production, and 3) test higher stoichiometric ratio between H₂ and CO/CO₂ to enhance syngas biomethanation efficiency. The data indicated higher methane content and syngas conversion in a semi-continuous mode. The biogas had methane concentration of 82.3, 76.9, 73.8, 84.9 and 81.7% in samples CO₂:CO: H₂ (1:1:7), CO:H₂ (1:3), CO₂:H₂ (1:4), CO: H₂ (1:4) and CO₂:H₂ (1:5). By injecting gas into the biomass in several stages, methane levels in the produced biogas in each stage increased, demonstrating the adaptation of microorganisms to the injected hydrogen and carbon-sourced gases. A higher stoichiometric ratio of H₂ to CO/CO₂ promoted the growth and activity of methanogens, leading to increased methane production.

The goal of this work was to establish the suitable and limiting concentrations of Zn, Cu and Mn compounds during syngas fermentation. The results showed that cells encased in polyvinylidene difluoride (PVDF) membranes had a faster accumulation of methane in reactors containing fermentation medium dosed with 5 mg/L of each heavy metal compared to free cells. It was also revealed that total inhibition of biohydrogen production occurred in medium containing 5 mg/L Cu, 30 mg/L Zn and 140 mg/L Mn while the most suitable metal concentration level was 0.1 mg/L Cu, 0.6 mg/L and 2.8 mg/L Mn. In addition, a comparison test showed that for the most suitable metal concentration in the medium, rate of performance at pH 6 and 7 was higher than at pH 5.

Comme dans les pays du Nord riches, il y a également une augmentation de la production de déchets organiques dans les pays du Sud moins avancés. Connues sous l'appellation de Matières Organiques Exogènes (MOEx), les déchets organiques peuvent être valorisables comme engrais ou amendement pour les sols agricoles ou bien une nouvelle source de biomasse pour la production d'énergie. L'utilisation raisonnée d'une MOEx exige toutefois une connaissance scientifique approfondie de leur nature et de leurs impacts sur l'environnement. Des analyses conventionnelles en laboratoire et des expérimentations doivent être effectués pour maîtriser leur structure complexe liée à leurs propriétés physiques, chimiques et biochimiques. Celles-ci sont généralement longues et onéreuses. Dans notre étude, la spectroscopie proche infrarouge (SPIR) a été choisie comme une alternative aux méthodes classiques pour la caractérisation de ces MOEx en milieu tropical humide. Les objectifs de notre travail sont (1) de montrer que la SPIR est une méthode appropriée pour la prédiction des caractéristiques de MOEx, (2) pour caractériser les MOEx en termes de leur potentiel agronomique et leur potentiel énergétique et (3) pour élaborer une typologie, construite à partir des données prédites par la SPIR, qui prend en compte quelques impacts négatifs liés à l'utilisation des MOEx. L'ensemble des données a inclus plus de 2000 échantillons de MOEx couvrant une large gamme de MOEx fraîches ou transformées issues de l'élevage, de la ville et des agroindustries. Le spectre SPIR de chaque EOM a été acquis. En plus des caractérisations classiques de laboratoire (les dosages de carbone, azote, phosphore, potassium, etc.), d'autres expérimentations ont été conduites en vue d’évaluer (1) les potentiels « positifs » des MOEx : (i) suivi de la minéralisation du carbone et de l'azote mesurée dans des conditions contrôlées pour une valorisation agronomique, (ii) détermination du pouvoir calorifique et du potentiel méthanogène pour une valorisation énergétique ; et (2) les potentiels « négatifs » des MOEx : (i) dénitrification potentielle et (ii) phytotoxicité en présence d’éléments trace métallique. Pour élaborer la typologie, la méthode SIRIS (Système d'Ingration des Risques par Interaction des Scores) a été appliquée pour formaliser les étapes d'une procédure logique menant à une classification des MOEx selon l'objectif de l'orientation de recyclage. La diversité des MOEx est illustrée à titre d'exemple par une large gamme des teneurs en (i) C (de 2 à 64 gC.100g-1MS), (ii) N (de 0,2 à 14gN.100g-1MS), (iii) P total (0,01 à 16gP.100g-1MS), K total (0,04 à 30 gK.100g-1MS). En prenant en compte l'ensemble des MOEx, les étalonnages des modèles SPIR sont acceptables pour la prédiction des teneurs en C, en N, en P et en K. Pour les potentiels « positifs » des MOEx (1) suivant les types de MOEx 102 à 955 kgMO.t-1MOEx pourraient être stockées dans le sol pour le maintien de la fertilité, (2) les pouvoirs calorifiques des MOEx varient de 7 à 28 MJ.kg-1MS et les potentiels méthanogènes vont de 69 à 488 NmlCH4.g-1MO. Quant aux potentiels négatifs, que ce soit pour les émissions de N2O ou pour la phytotoxicité des ETM, une forte interaction entre les propriétés du sol (pH, texture, …) avec les MOEx masque souvent certains effets. La méthode SIRIS a permis de classifier les MOEx selon un processus simple basé sur le classement de critères et de scores d'auto-pénalisation. Cette approche est intéressante en l'absence de données précises qui sont souvent difficiles à obtenir. L'aide des prédictions par la SPIR nous a été utile pour cette démarche d'orientation de la valorisation agronomique et/ou énergétique des MOEx. Des approches socio-économiques devraient compléter notre étude pour aboutir à l'orientation finale de valorisation des MOEx. / As observed in northern/rich countries, there is an increase in the production of organic wastes in southern/less advanced countries. So called, Exogenous Organic Matter (EOM), they can be a valuable fertilizer or amendment for agricultural soils or a new supply for energy production. The safe utilisation of EOM requires an in-depth scientific knowledge of their nature and impacts on the environment. Laboratory analysis and experiments have to be carried out in order to know their complex structure related to their physical, chemical and biochemical properties. These techniques represent a relatively high cost and are time consuming. In this study, the near infrared spectroscopy (NIRS) was chosen as an alternative to classical methods for laboratory characterisations of tropical EOM. The objectives of this study are (1) to show that NIRS is a suitable method for predicting EOM characteristics (2) to characterize EOM in terms of their agronomic potential and/or energetic potential, and (3) to elaborate a typology, build with predicted parameters by NIRS, taking into account some environmental impacts of the different utilisations of EOM.The dataset included more than 2000 EOM samples covering a broad range of fresh and transformed organic materials. Each EOM was scanned using a NIR spectrometer from 1100nm to 2500nm. In addition to the classical laboratory characterisations (dosages of total carbon, nitrogen, phosphorus, potassium), other experiments have been carried out: (1) for “positive” potentials: (i) C and N mineralization measured in controlled conditions (for an agronomic use), (ii) determination of High Heating Value and Biochemical Methane Potential (for an energetic use) and (2) for “negative” potential or risk: phytotoxicity assessment due to trace elements, and the determination of potential nitrous oxide emission. To elaborate the typology, the SIRIS method (System of Integration of Risk with Interaction of Scores) was carried out in order to formalize the steps of a logical procedure, leading to a decision according to objective of the recycling orientation.Diversity of EOM is illustrated by the variability of (i) C contents (from 2 to 64 gC.100g-1DM); (ii) N contents (from 0.2 to 14gN.100g-1DM); (iii) total P contents (from 0.01 to 16gP.100g-1DM),(iv) total K contents (from 0.04 to 30 gK.100g-1DM). When taking into account all EOM without regarding their nature, acceptable predictive models were obtained with NIRS calibration for estimating C, N, total P and total K contents for EOM.“Positive” potential assessment provided information about (1) remaining organic carbon might be stocked into soil after applying EOM (from 102 to 955 kg.t-1TOM) (2) High Heating Value of EOM when recycling as a supply of small scale combustion or thermo chemical conversion (from 7 to 28 MJ.kg-1DM), (3) Biochemical Methane Potential after EOM anaerobic digestion (from 69 to 488 NmlCH4.g-1TOM). Both “negative” potential which took into account phytotoxicity due to trace elements and nitrous oxide emissions were highly interacted on the soil properties (pH, texture). The SIRIS method appeared to be an efficient decision-making tool in this study. It made it possible to classify the EOM according to a simple process based on the ranking of criteria and a self-penalization scoring system. This approach can be used in the absence of accurate, reliable data, which are often difficult to obtain. The help of NIR prediction was useful for better orientate the EOM valorization between soil fertilization and energy production. Further concern will be focused on socio-economical approach in order to complete the final destination of EOM re-use.

O modo de vida da humanidade demanda novas alternativas às fontes energéticas fósseis, precisa garantir a produção de alimentos e energia para uma população que já ultrapassa 7 bilhões, além de ter de gerir seus Resíduos Sólidos (RS) e efluentes (esgoto), em que grande parte dos primeiros, são enterrados em aterros sanitários e/ou lixões, gerando problemas sanitários e ambientais e desperdício de nutrientes para a agricultura. Parte dessa tripla solução energética/alimentar/sanitária pode vir dos recursos contidos nos Resíduos Biodegradáveis (RB), ou como dito na Lei Brasileira Nº 12.305 - "Resíduos Orgânicos" (RO), que podem ser biometanizados para gerar gás combustível, metano, CH4 e/ou gás hidrogênio, H2 e posterior uso do sólido e líquido resultante na forma de substrato para a agricultura, ou processos fotossintéticos aquáticos mediados por microalgas e macrófitas. Paralelamente ao tratamento anaeróbio, se os RO forem tratados aerobicamente, via compostagem e/ou vermicompostagem, não se gera nenhum gás combustível que possa ser usado em outro momento e local, apenas calor. Diante desse quadro, se propõe uma alternativa para o tratamento de resíduos biodegradáveis e efluentes domésticos em zonas rurais e periurbanas, por meio da proposta de uma pequena central de tratamento de resíduos orgânicos composta por uma lagoa facultativa com geração e coleta de biogás, associada com um sistema de hidrolisação de resíduos sólidos orgânicos e de tratamento de biogás, havendo a separação do CO2 em fase aquosa para alimentação de carbono e alcalinidade ao sistema de bacia de fotossíntese de microalgas e macrófitas do gênero lemna. Foram realizados balanços de água, nutrientes, eletricidade e monetário para aferir a consistência teórica para futura aplicação dos projetos e suprir as três demandas/soluções citadas. Foi possível aferir que o custo do metro cúbico de gás metano gerado ficou em torno de 0,5- 4 R$.m-3 de gás metano. Foi possível propor um projeto para se caminhar no sentido de poder dar base a trabalhos futuros, que desenvolvam métodos inovadores de gestão de resíduos para serem aplicados no Brasil, com o fim de descentralizadamente adequar os municípios ao PNRS, ao mesmo tempo em que se cria na nação o conceito de biorrefinaria, integrando-a ao saneamento básico e ambiente, em prol da soberania individual energética/alimentar/hidrológica dos brasileiros. / People's way of living demands alternatives to fossil energy, needs to produce food for a population that has already reached more than seven billion and has to deal with waste generation, namely solid wastes and sewage, while most of the first are buried in landfills or even dumped, generating sanitary and environmental problems while wasting nutrients for agriculture. Part of that triple energy/food/sanitation solution can come from biodegradable wastes, or like the way is said on Brazilian Law Nº12.305 - &#34Organic Wastes", that can be converted into biogas, methane or hydrogen gas, and subsequent use of solid and liquid digestate for agriculture, or aquatic photosynthetic processes mediated by microalgae and macrophytes. Paralel to anaerobic treatment, if organic wastes are aerobically treated, by compoting and/or wormcomposting, not any renewable gas will be generated for later use, it just generates heat. By this cenario, this master thesis propose and evaluate, technological alternatives for biodegradable waste and wastewaters in cities vicinities and/or rural areas nearby urban areas by proposing a small biodegradable waste treatment plant composed of a facultative lagoon with biogas generation on its bottom, associated with a system of solid waste hydrolysis built inside a shed which realizes biogas treatment as well, with carbon dioxide gas liquid separation for carbon and alkalinity feeding the multispecies photosynthesis bowl, half consisted of dispersed microalgae and the other half composed of macrophyte of lemna genera. Water, nutrients, electricity and money balances were done in order assess the theoretical consistency for future development of those projects and quench the three cited demands/solutions. It was possible to affirm that the cost of a cubic meter of methane gás is around 0,5 – 4 R$.m-3. Projects were proposed, that can develop innovative methods for biodegradable waste management to be done in Brazil, with the ultimate goal of adequating towns to the National Solid Waste Policy (Política Nacional de Resíduos Sólidos – PNRS in portuguese) in a decentralized manner, meanwhile it helps to create alog the nation the biorefinery concept, integrating itself into waterworks, sanitation and the environment, feeding individuals energy, food and hydrological sovereignity of brazilians.

O modo de vida da humanidade demanda novas alternativas às fontes energéticas fósseis, precisa garantir a produção de alimentos e energia para uma população que já ultrapassa 7 bilhões, além de ter de gerir seus Resíduos Sólidos (RS) e efluentes (esgoto), em que grande parte dos primeiros, são enterrados em aterros sanitários e/ou lixões, gerando problemas sanitários e ambientais e desperdício de nutrientes para a agricultura. Parte dessa tripla solução energética/alimentar/sanitária pode vir dos recursos contidos nos Resíduos Biodegradáveis (RB), ou como dito na Lei Brasileira Nº 12.305 - "Resíduos Orgânicos" (RO), que podem ser biometanizados para gerar gás combustível, metano, CH4 e/ou gás hidrogênio, H2 e posterior uso do sólido e líquido resultante na forma de substrato para a agricultura, ou processos fotossintéticos aquáticos mediados por microalgas e macrófitas. Paralelamente ao tratamento anaeróbio, se os RO forem tratados aerobicamente, via compostagem e/ou vermicompostagem, não se gera nenhum gás combustível que possa ser usado em outro momento e local, apenas calor. Diante desse quadro, se propõe uma alternativa para o tratamento de resíduos biodegradáveis e efluentes domésticos em zonas rurais e periurbanas, por meio da proposta de uma pequena central de tratamento de resíduos orgânicos composta por uma lagoa facultativa com geração e coleta de biogás, associada com um sistema de hidrolisação de resíduos sólidos orgânicos e de tratamento de biogás, havendo a separação do CO2 em fase aquosa para alimentação de carbono e alcalinidade ao sistema de bacia de fotossíntese de microalgas e macrófitas do gênero lemna. Foram realizados balanços de água, nutrientes, eletricidade e monetário para aferir a consistência teórica para futura aplicação dos projetos e suprir as três demandas/soluções citadas. Foi possível aferir que o custo do metro cúbico de gás metano gerado ficou em torno de 0,5- 4 R$.m-3 de gás metano. Foi possível propor um projeto para se caminhar no sentido de poder dar base a trabalhos futuros, que desenvolvam métodos inovadores de gestão de resíduos para serem aplicados no Brasil, com o fim de descentralizadamente adequar os municípios ao PNRS, ao mesmo tempo em que se cria na nação o conceito de biorrefinaria, integrando-a ao saneamento básico e ambiente, em prol da soberania individual energética/alimentar/hidrológica dos brasileiros. / People's way of living demands alternatives to fossil energy, needs to produce food for a population that has already reached more than seven billion and has to deal with waste generation, namely solid wastes and sewage, while most of the first are buried in landfills or even dumped, generating sanitary and environmental problems while wasting nutrients for agriculture. Part of that triple energy/food/sanitation solution can come from biodegradable wastes, or like the way is said on Brazilian Law Nº12.305 - &#34Organic Wastes", that can be converted into biogas, methane or hydrogen gas, and subsequent use of solid and liquid digestate for agriculture, or aquatic photosynthetic processes mediated by microalgae and macrophytes. Paralel to anaerobic treatment, if organic wastes are aerobically treated, by compoting and/or wormcomposting, not any renewable gas will be generated for later use, it just generates heat. By this cenario, this master thesis propose and evaluate, technological alternatives for biodegradable waste and wastewaters in cities vicinities and/or rural areas nearby urban areas by proposing a small biodegradable waste treatment plant composed of a facultative lagoon with biogas generation on its bottom, associated with a system of solid waste hydrolysis built inside a shed which realizes biogas treatment as well, with carbon dioxide gas liquid separation for carbon and alkalinity feeding the multispecies photosynthesis bowl, half consisted of dispersed microalgae and the other half composed of macrophyte of lemna genera. Water, nutrients, electricity and money balances were done in order assess the theoretical consistency for future development of those projects and quench the three cited demands/solutions. It was possible to affirm that the cost of a cubic meter of methane gás is around 0,5 – 4 R$.m-3. Projects were proposed, that can develop innovative methods for biodegradable waste management to be done in Brazil, with the ultimate goal of adequating towns to the National Solid Waste Policy (Política Nacional de Resíduos Sólidos – PNRS in portuguese) in a decentralized manner, meanwhile it helps to create alog the nation the biorefinery concept, integrating itself into waterworks, sanitation and the environment, feeding individuals energy, food and hydrological sovereignity of brazilians.

Au cours des dernières décennies, l’intérêt pour la gazéification de biomasses a considérablement augmenté, notamment en raison de la grande efficacité de recouvrement énergétique de ce procédé par rapport aux autres procédés de génération de bioénergies. Les composants majoritaires du gaz de synthèse, le monoxyde de carbone (CO) et l’hydrogène (H2) peuvent entre autres servir de substrats à divers microorganismes qui peuvent produire une variété de molécules chimiques d’intérêts, ou encore produire des biocarburants, particulièrement le méthane. Il est donc important d'étudier les consortiums méthanogènes naturels qui, en syntrophie, serait en mesure de convertir le gaz de synthèse en carburants utiles. Cette étude évalue principalement le potentiel de méthanisation du CO par un consortium microbien issu d’un réacteur de type UASB, ainsi que les voies métaboliques impliquées dans cette conversion en conditions mésophiles. Des tests d’activité ont donc été réalisés avec la boue anaérobie du réacteur sous différentes pressions partielles de CO variant de 0.1 à 1,65 atm (0.09 à 1.31 mmol CO/L), en présence ou absence de certains inhibiteurs métaboliques spécifiques. Dès le départ, la boue non acclimatée au CO présente une activité carboxidotrophique relativement intéressante et permet une croissance sur le CO. Les tests effectués avec de l’acide 2- bromoethanesulfonique (BES) ou avec de la vancomycine démontrent que le CO est majoritairement consommé par les bactéries acétogènes avant d’être converti en méthane par les méthanogènes acétotrophes. De plus, un plus grand potentiel de méthanisation a pu être atteint sous une atmosphère constituée uniquement de CO en acclimatant auparavant la boue. Cette adaptation est caractérisée par un changement dans la population microbienne désormais dominée par les méthanogènes hydrogénotrophes. Ceci suggère un potentiel de production à large échelle de biométhane à partir du gaz de synthèse avec l’aide de biofilms anaérobies. / Syngas produced through the thermal gasification of biomass for energy recovery has received increased attention in the past decades due to its higher efficiency compared to other bioenergy processes. The gas components of syngas, CO and H2, can serve as substrates for the conversion of desirable chemicals and fuels, namely methane, by a wide range of microorganisms. Meanwhile, anaerobic wastewater-treating sludges have been reported as good sources of carboxidotrophic microorganisms which can be exploited for methane production. Thus it is important to investigate existing methanogenic consortiums which, in syntrophy, are able to convert syngas into useful fuels. This study is mainly focused on the assessment of the carboxidotrophic methanogenic potential present in a natural consortium of microorganisms from a UASB reactor and the identification of CO conversion routes to methane under mesophilic temperatures. To achieve this, a series of kinetic-activity tests with the anaerobic sludge were performed under CO partial pressures varying from 0.1 to 1.65 atm (0.09-1.31 mmol/L) in both the presence and absence of specific metabolic inhibitors. The non-adapted sludge presented an interesting carboxidotrophic activity potential for growing conditions on CO alone. Inhibition experiments with 2- bromoethanesulfonic acid (BES) and vancomycin showed that CO was converted mainly to acetate by acetogenic bacteria, which was further transformed to methane by acetoclastic methanogens. Moreover, it was possible to achieve higher methanogenic potential under 100% CO by acclimation of the sludge. This adaptation led to a shift in the microbial population predominated by hydrogenophilic methanogens. This suggests a possible enrichment potential with anaerobic biofilms for large scale methane production from CO-rich syngas, and further advances the knowledge base for anaerobic reactor development.

Au cours des dernières décennies, l’intérêt pour la gazéification de biomasses a considérablement augmenté, notamment en raison de la grande efficacité de recouvrement énergétique de ce procédé par rapport aux autres procédés de génération de bioénergies. Les composants majoritaires du gaz de synthèse, le monoxyde de carbone (CO) et l’hydrogène (H2) peuvent entre autres servir de substrats à divers microorganismes qui peuvent produire une variété de molécules chimiques d’intérêts, ou encore produire des biocarburants, particulièrement le méthane. Il est donc important d'étudier les consortiums méthanogènes naturels qui, en syntrophie, serait en mesure de convertir le gaz de synthèse en carburants utiles. Cette étude évalue principalement le potentiel de méthanisation du CO par un consortium microbien issu d’un réacteur de type UASB, ainsi que les voies métaboliques impliquées dans cette conversion en conditions mésophiles. Des tests d’activité ont donc été réalisés avec la boue anaérobie du réacteur sous différentes pressions partielles de CO variant de 0.1 à 1,65 atm (0.09 à 1.31 mmol CO/L), en présence ou absence de certains inhibiteurs métaboliques spécifiques. Dès le départ, la boue non acclimatée au CO présente une activité carboxidotrophique relativement intéressante et permet une croissance sur le CO. Les tests effectués avec de l’acide 2- bromoethanesulfonique (BES) ou avec de la vancomycine démontrent que le CO est majoritairement consommé par les bactéries acétogènes avant d’être converti en méthane par les méthanogènes acétotrophes. De plus, un plus grand potentiel de méthanisation a pu être atteint sous une atmosphère constituée uniquement de CO en acclimatant auparavant la boue. Cette adaptation est caractérisée par un changement dans la population microbienne désormais dominée par les méthanogènes hydrogénotrophes. Ceci suggère un potentiel de production à large échelle de biométhane à partir du gaz de synthèse avec l’aide de biofilms anaérobies. / Syngas produced through the thermal gasification of biomass for energy recovery has received increased attention in the past decades due to its higher efficiency compared to other bioenergy processes. The gas components of syngas, CO and H2, can serve as substrates for the conversion of desirable chemicals and fuels, namely methane, by a wide range of microorganisms. Meanwhile, anaerobic wastewater-treating sludges have been reported as good sources of carboxidotrophic microorganisms which can be exploited for methane production. Thus it is important to investigate existing methanogenic consortiums which, in syntrophy, are able to convert syngas into useful fuels. This study is mainly focused on the assessment of the carboxidotrophic methanogenic potential present in a natural consortium of microorganisms from a UASB reactor and the identification of CO conversion routes to methane under mesophilic temperatures. To achieve this, a series of kinetic-activity tests with the anaerobic sludge were performed under CO partial pressures varying from 0.1 to 1.65 atm (0.09-1.31 mmol/L) in both the presence and absence of specific metabolic inhibitors. The non-adapted sludge presented an interesting carboxidotrophic activity potential for growing conditions on CO alone. Inhibition experiments with 2- bromoethanesulfonic acid (BES) and vancomycin showed that CO was converted mainly to acetate by acetogenic bacteria, which was further transformed to methane by acetoclastic methanogens. Moreover, it was possible to achieve higher methanogenic potential under 100% CO by acclimation of the sludge. This adaptation led to a shift in the microbial population predominated by hydrogenophilic methanogens. This suggests a possible enrichment potential with anaerobic biofilms for large scale methane production from CO-rich syngas, and further advances the knowledge base for anaerobic reactor development.

Polymer hydrolysis is the first (and rate limiting) step for biomethanation of heterogeneous biomass feedstock’s. Satisfactory hydrolysis has been difficult to achieve, understand and predict adequately, to run anaerobic bioreactors with such feedstock’s efficiently. The fraction of hot water soluble extracts (crude proteins and extractables, Fcpe), the nature and material of intercellular binding and the extent and complexity of lignin present have been considered as key parameters for hydrolysis and has been analyzed for a variety of biomass degradation data available at the Centre for Sustainable Technologies, Indian Institute of Science. Feedstocks were grouped into those bound with high levels of pectic/protein materials or lignin-bound types. The data on the initial (10-15d) as well as the overall rates of hydrolysis (0-50d) has been analyzed. The extent of hydrolysis achieved for pectin bound substrates were high (≥65%) and that of lignin bound substrate was low (≤30% VS, Acacia). The initial hydrolysis rates were strongly correlated to the content of extractables (=0.117Fcpe). Subsequently, the hydrolysis rates rise to reach maxima and then begin to fall. Most fresh feedstock had somewhat similar rates of the increase in hydrolysis rates but the time to reach maximum and its value varied among feed stocks. Many lignin bound feed stocks did not have such a pattern. With regards to the overall hydrolysis rate constant, it was found that these clustered into two groups that represented pectin bound (0.154/d) and lignin bound (0.045/d) types. Therefore from this study it was concluded that anaerobic decomposition of heterogeneous biomass could be predicted using two rate parameters and one intrinsic property of the biomass feedstock, namely, a. the initial rate of hydrolysis (based on the extent of extractables =0.117 Fcpe) b.the maximum rate achieved and the time when it is reached (an intrinsic property based on feed stock and but not determined in this study) c. the overall hydrolysis rate (choosing between 0.154 /d or 0.045 /d depending upon the nature of inter-cellular binding material, pectin or lignin, respectively). This research provides new insights into the prediction of hydrolysis rate a key limiting step for heterogeneous biomass biomethanation (hydrolysis) based on the level of extractables, the type of cellular cementing material and the maxima that can be achieved.

Im Laborversuch konnte der positive Einfluss einer thermobarischen Vorbehandlung auf die Hydrolysier- und Vergärbarkeit von Rinderfestmist und Rindergülle nachgewiesen werden. Die Laborergebnisse wurden innerhalb eines theoretischen Modells in den Praxismaßstab übertragen, um den Einfluss auf Treibhausgasemissionen, Energiebilanz und Ökonomie zu bewerten. Die Vorbehandlungstemperaturen im Labor lagen zwischen 140 und 220°C in Schritten von 20 K und einer Vorbehandlungszeit von jeweils 5 Minuten. Die höchste Methanmehr¬ausbeute von 58 % konnte bei einer Temperatur von 180°C ermittelt werden. Das Auftreten von Inhibitoren und nicht vergärbaren Bestandteilen führte bei einer Aufbereitungstemperatur von 220°C zu Methanausbeuten, die geringer waren als die des unaufbereiteten Einsatzstoffes. In einer erweiterten Analyse konnte ein funktioneller Zusammenhang zwischen der Methanausbeute nach 30 Tagen und der Methanbildungsrate und -ausbeute während der Beschleunigungsphase gezeigt werden. Mittels einer Regressionsanalyse der so ermittelten Werte wurde nachgewiesen, dass die optimale Aufbereitungstemperatur 164°C ist und die minimale größer als 115°C zu sein hat. Treibhausgasemissionen und Energiebilanz wurden im Rahmen einer Ökobilanz nach ISO 14044 (2006) ermittelt, sowie eine Kosten-Nutzen-Analyse durchgeführt. Dazu wurde eine Anlage zur thermobarischen Vorbehandlung entwickelt und innerhalb eines Modells in eine Biogasanlage integriert. Weiterhin wurde in diesem Modell Maissilage durch Rinderfestmist und / oder Rindergülle als Einsatzstoff ersetzt. Rinderfestmist, ein Einsatzstoff mit hohem organischen Trockenmassegehalt, der ohne Vorbehandlung nicht einsetzbar wäre, erreichte eine energetische Amortisationszeit von 9 Monaten, eine Vermeidung in Höhe der während der Herstellung emittierten Treibhausgase innerhalb von 3 Monaten und eine ökonomische Amortisationszeit von 3 Jahren 3 Monaten, wohingegen Rindergülle keine positiven Effekte zeigte. / Hydrolysis and digestibility of cattle waste as feedstock for anaerobic digestion were improved by thermobarical treatment in lab-scale experiments. The effects of this improvement on greenhouse gas emissions, energy balance and economic benefit was assessed in a full-scale model application. Thermobarical treatment temperatures in lab-scale experiments were 140 to 220°C in 20 K steps for a 5-minute duration. Methane yields could be increased by up to 58 % at a treatment temperature of 180°C. At 220°C, the abundance of inhibitors and other non-digestible substances led to lower methane yields than those obtained from untreated material. In an extended analysis, it could be demonstrated that there is a functional correlation between the methane yields after 30 days and the formation rate and methane yield in the acceleration phase. It could be proved in a regression of these correlation values that the optimum treatment temperature is 164°C and that the minimum treatment temperature should be above 115°C. The theoretical application of a full-scale model was used for assessing energy balance and greenhouse gas emissions following an LCA approach according to ISO 14044 (2006) as well as economy. A model device for thermobarical treatment has been suggested for and theoretically integrated in a biogas plant. The assessment considered the replacement of maize silage as feedstock with liquid and / or solid cattle waste. The integration of thermobarical pretreatment is beneficial for raw material with high organic dry matter content that needs pretreatment to be suitable for anaerobic digestion: Solid cattle waste revealed very short payback times, e.g. 9 months for energy, 3 months for greenhouse gases, and 3 years 3 months for economic amortization, whereas, in contrast, liquid cattle waste did not perform positive replacement effects in this analysis.

Municipal solid waste (MSW) production has significantly increased in the rapidly urbanizing developing world and also changed composition with increased decomposable organic fraction in MSW (OFMSW) and plastics content. This has stressed the environment in many ways while city managers and citizens have responded with various technological and management solutions leading to a need for scientific, environmental, technological and sustainability assessments of the emerging problems. This sets the research agenda and framework for this study wherein the MSW generation, composition, processing and treatment methods, open dumping practices, environmental liability, natural degradation, sustainability issues etc. have been studied for the city of Bangalore as a model for such an emerging problem. Results show that MSW generation ranged from 0.1-0.4 kg/person/day and the OFMSW content was >80% emerging predominantly from fruit, vegetable and food wastes. About 10-15% of daily MSW generated appeared to be haphazardly dumped around the city in ~700 small to large dumps ranging from 10-6,500 m2 with potential for large GHG emissions. Their spread and characteristics were assessed for 3 consecutive years using a novel rapid survey method developed at IISc involving motorcycle borne student volunteer teams, GPS enabled locating, physical measurements and satellite image interpretations. Results indicated that dump sites were of three types, ephemeral small sized in the core area (303) functioning as transfer stations, medium sized ones in outer areas that were closed rapidly with construction debris and very soon inhabited with dwellings and the larger and longer duration dumps (2-3 years, 393) in the peripheral regions within 10 km from the city administrative boundary. This method was compared with physical measurement and satellite imaging and gave very high level of accuracy and is hence suggested for other cities as well. A smaller fraction of MSW is also dumped in open drains that lead to choking and flooding of 3 locations and this was studied with some detail. The environmental footprint of such dumps were assessed by theoretical and experimental on-site and off-site approaches and experimental results show low GHG (CH4) emissions and emission factors that was largely attributable to the shallow depth of dumps (~0.7 m) and its low pH. The decomposition rates were experimentally determined for open dump sites and drivers for decomposition monitored. By providing differential access to macro-fauna, meso-micro organisms and only soil contact in field scale experiments it was determined that the greatest loss in weight occurred primarily due to the rapid drying process that brings down decomposition within 6 days. During the early stages of decomposition, mostly micro with meso organisms are responsible and after 6 days, the moisture content falls below 60% making microbiological decomposition difficult and enabling other foraging organisms to take over. The weight loss (decay) could be patterned both on exponential decay or a two component fit representing a rapid initial decay followed by a slower long term decay process similar to soil application of organic matter. Monitoring the decentralized MSWM practices in the city suggests that small scale composting and biomethanation is gaining acceptance and is the possible direction for OFMSW in growing cities.