Thesis: Ph. D., Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Department of Civil and Environmental Engineering; and the Woods Hole Oceanographic Institution), 2015. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Microorganisms play a central role mediating biogeochemical cycles in the ocean. Marine dissolved organic matter (DOM) - a reservoir of organic solutes and colloids derived from plankton is a major source of carbon, nutrients, and energy to microbial communities. The biological transformation and remineralization of DOM sustains marine productivity by linking the microbial food web to higher trophic levels (the microbial loop) and exerts important controls over the cycles of carbon and bioessential elements, such as nitrogen and phosphorus, in the sea. Yet insight into the underlying metabolism and reactions driving the degradation of DOM is limited partly because its exact molecular composition is difficult to constrain and appropriate microbial model systems known to decompose marine DOM are lacking. This thesis identifies marine microorganisms that can serve as model systems to study the metabolic pathways and biochemical reactions that control an important ecosystem function, DOM turnover. To accomplish this goal, bacterial isolates were obtained by enriching seawater in dilution-to-extinction culturing experiments with a natural source of DOM, specifically, the high molecular weight (HMW) fraction (>1 kDa nominal molecular weight) obtained by ultrafiltration. Because it is relatively easy to concentrate and it is fairly uniform in its chemical composition across the global ocean and other aquatic environments, HMW DOM has the potential to serve as a model growth substrate to study the biological breakdown of DOM. The phylogeny, genomes, and growth characteristics of the organisms identified through this work indicate that HMW DOM contains bioavailable substrates that may support widespread microbial populations in coastal and open-ocean environments. The availability of ecologically relevant isolates in culture can now serve to test hypothesis emerging from cultivation-independent studies pertaining the potential role of microbial groups in the decomposition of organic matter in the sea. Detailed studies of the biochemical changes exerted on DOM by selected bacterial strains will provide new insight into the processes driving the aerobic microbial food chain in the upper ocean. / by Oscar Abraham Sosa. / Ph. D.

[pt] A compostagem apresenta-se como um dos principais tratamentos e destino para os resíduos orgânicos, entretanto na área urbana tem sido utilizada em pequena escala, pois grande parte desta fração é disposta diretamente em aterros sanitários. Associada à grande oferta de matéria orgânica e a fim de incentivar a adoção desta prática nas cidades, torna-se interessante aliá-la às hortas urbanas, visto que o produto gerado no processo auxilia na fertilidade e fornece nutrientes ao solo. Este trabalho pretendeu testar diferentes misturas de resíduos vegetais em um processo de compostagem em leiras estáticas com aeração passiva realizado dentro de um ambiente urbano com intuito de avaliar os compostos produzidos. A pesquisa se deu por meio de experimento de campo, o qual foi conduzido no campus da PUC-Rio, na cidade do Rio de Janeiro, entre novembro de 2018 e março de 2019. O experimento foi constituído por leiras com 3 diferentes composições e 2 repetições. As misturas foram folha + grama, folha + grama + galho e folha + galho. As matérias-primas foram pesadas no início e no fim do processo. Os compostos produzidos foram pesados e amostras foram levadas para análise em laboratório. A mistura folha + grama foi a mais produtiva; a mistura folha + grama + galho apresentou, em geral, os resultados analíticos mais altos, porém não houve grandes diferenças entre as misturas. Todos os compostos apresentaram resultados satisfatórios e de acordo com padrões existentes em literatura e legislação brasileira relacionada. A metodologia se mostrou eficiente. / [en] Solid waste is a problem, some consequences and negative environmental impacts of its generation and wrong disposal are inappropriate treatment; waste dumps disposal; emissions; air, soil and water pollution; a threat to marine biodiversity; incorporated hazardous substances. In Brazil in 2017, circa 42,3 million tons of MSW collected, equivalent of 59,1 percent, was disposed in sanitary landfill. The rest, 40,9 percent, more than 29 million tons, was disposed in inappropriate places, such as waste dumps and controlled landfills (ABRELPE, 2018). In the country, more than the half of the MSW, 51,4 percent, consists in organic matter (Brasil, 2012). This material is often disposed together with other types of waste. It influences the production of methane from landfills and reduces its lifespan. A very good management, separate collection systems, searching alternatives to give this material a better destination and treatment is necessary. An alternative of treatment to organic waste is composting, a simple and good technology. It is a biological process that occurs mainly by microorganisms action, decomposition of organic matter, such as food scraps, fruits, leaves and manure. The product of the process is the compost, a stable material that is dark brown or black and has an earthy smell, rich in nutrients, able to improve physical, chemical and biological qualities of the soil and may be used in agriculture (Souza et al., 2001; Nunes, 2009). Composting is a useful technique for organic waste management in urban and industrial areas, agricultural use and sustainable development, a satisfactory process for waste treatment (Oliveira et al., 2008; Inácio and Miller, 2009). The high generation of organic waste shows the potential of material able to be treated. According to Leal (2014), the use of these materials is fundamental to cause sustainability of national agriculture and environmental conservation. Thus, avoiding materials from accumulating in a certain location, which can cause environmental problems, taking them to other places for agricultural and plant production. There is in Brazil a specific law for solid waste, it is the law number 12.305 of 2010, that institutes the National Policy on Solid Waste (Política Nacional de Resíduos Sólidos – PNRS, in Portuguese). It defines terms and sets goals. The law mentions composting as a final environmentally adequate destination and that it should be implemented a composting system for organic waste (Brasil, 2010).

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L'emballage alimentaire est l'un des principaux acteurs de la préservation de la sécurité alimentaire et de la qualité au cours du stockage. Toutefois, de transferts de masse se produisent entre le l'emballage polymère et les denrées alimentaires. Polylactide (PLA) est un nouveau polymère biosourcé utilisé dans les applications d'emballage. Pour cela son interaction avec des denrées alimentaires a été étudiée dans des conditions réelles d'utilisation. Une méthodologie originale basée sur l'extraction multiple de l'espace de tête (MHE) et l'extraction multiple de l'espace de tête couplée à la microextraction sur phase solide (MHS-SPME) pour la mesure de sorption de composés organiques volatils (COVs) dans le PLA a été développé à des activités faibles et dans le domaine vitreux du polymère. Les COVs ayant une structure chimique modérément hydrophobe et des similarités de structure avec le PLA montrent une forte affinité pour le polymère. Plus surprenant, la forte sorption de composés aromatiques, notamment du benzaldéhyde, a été montrée. En mélange avec d'autres COVs le benzaldéhyde favorise leur sorption par un effet synergique. De plus, même à des activités faibles (0,01) et en présence de benzaldéhyde, la sorption de COVs induit une cristallisation du PLA. En contact avec un aliment aqueux, le PLA se montre résistant à l'hydrolyse et la sorption des matières grasses est faible, même en utilisant des conditions de stockage proches de sa transition vitreuse. L'apparition de COVs pendant le procédé de transformation a été étudiée par MHS-SPME. Des lactides, l'acétaldéhyde et le 2,3-pentanedione étaient détectés après extrusion et thermoformage. Les quantités des deux derniers composés diminuaient cependant pendant le procédé de thermoformage. / Packaging plays a major role in the preservation of food but mass transfer between the packaging material and foodstuff occurs during shelf life leading to the quality deterioration. Polylactide (PLA) is a novel packaging material; therefore its interaction with food was investigated at service conditions. The sorption of ethyl esters, benzaldehyde and 2-nonanone at low concentrations and in mixture and the effects on the thermal properties of PLA were studied. Multiple Headspace Extraction (MHE) and Multiple Headspace coupled to Solid Phase MicroExtraction (MHS-SPME) developed here allow to show a high affinity for moderately hydrophilic molecules sharing structure similarities with PLA such as ethyl acetate. However, a very high affinity for the aromatic structure of benzaldehyde was revealed which seems to favor interaction and sorption of the aroma compounds present in the mixture. At 0.01 activities, a plasticization by aroma compounds was observed and a solvent induced crystallization seemed to be correlated to the sorption of benzaldehyde. The contact between a flavored food emulsion and PLA, using conditions near the PLA glass transition showed that PLA hydrolysis was moderate and oil and aroma compound sorption was low. The formation of VOC during the PLA manufacturing process was assessed by MHS-SPME. Lactides, acetaldehyde and 2,3-pentanedione are VOCs present in PLA after extrusion and thermoforming. The two latter compounds increased after extrusion and then decreased or disappeared after thermoforming.

[pt] O liner é um elemento de extrema importância no processo construtivo de um aterro sanitário, pois funciona como uma barreira capaz de impedir a percolação de agentes contaminantes através do subsolo. Os liners ou camadas impermeabilizantes são geralmente construídos a partir de materiais que possuem baixa permeabilidade. A escolha de um material adequado, assim como o controle dos processos construtivos são indispensáveis para garantir um bom desempenho da camada impermeabilizante. O processo de compactação é de extrema importância neste tipo de obra geotécnica. Os ensaios de compactação realizados em laboratório têm como objetivo reproduzir as condições de campo, no entanto, em numerosos casos há diferenças importantes entre os mecanismos de compactação utilizados, na preparação do material antes do processo de densificação e nas características das amostras, o que gera como conseqüência discrepâncias nos valores de permeabilidade de campo com os de laboratório. O objetivo principal do presente estudo é avaliar experimentalmente a influência de dois mecanismos diferentes de compactação (dinâmico, com o Proctor Normal e estático, com o método de compactação por pisoteamento) nos valores de permeabilidade de um solo coluvionar e de um composto orgânico para seu eventual uso em um liner. Os ensaios foram realizados em corpos de prova com diferentes teores de umidade, preparados com solo coletado no campo Experimental II da PUC-Rio, com composto orgânico produzido a partir do processo de compostagem da grama do Aeroporto Internacional Galeão (RJ), e com misturas em diferentes proporções de ambos os materiais. / [en] The liner is one of the most important elements in a sanitary landfill project, since it works as a barrier capable to impede seepage of pollutant substances through the subsurface. This element is usually built with materials that have low permeability. The choice of the right material as well as the control and supervision of the constructive processes are fundamental to achieve a good liner performance. The compaction process is extremely important in this type of geotechnical impoundment. Laboratory compaction intends to reproduce the field conditions; however, in some cases, there happen to be important differences between the compaction mechanisms used, the preparation of the material before the densification process and the specimens characteristics, which cause discrepancies between the permeability values obtained in the field and the ones obtained in the laboratory. The main objective of this study is to evaluate experimentally the effect of two different compaction mechanisms (dynamic, with standard Proctor and static, with the kneading compaction method) in the hydraulic conductivity of a colluvionar soil and an organic compound for their eventual use in a liner. The tests were executed using specimens with different water contents, prepared with colluvionar soil extracted from the Experimental Field II at the PUC-Rio, with the organic compound, and with mixtures of both materials in different proportions.

A quantificação de 11 compostos carbonílicos (formaldeído, acetaldeído, acetona, acroleína, propionaldeído, crotonaldeído, butiraldeído, benzaldeído, isovaleraldeído, valeraldeído e 2,5-dimetilbenzaldeído) e a identificação de outros 43 compostos orgânicos voláteis (alcanos, alcenos, aromáticos, halogenados e nitrogenados) foram feitas em 9 ambientes diferentes de trabalho localizados em áreas internas do Hospital Universitário, USP, São Paulo. Dentre os compostos carbonílicos, os mais abundantes em ordem decrescente foram formaldeído, acetona, acetaldeído e acroleína. As maiores razões de mistura de formaldeído foram observadas nas salas de Macroscopia (169,9 e 90,2 ppbv) e Técnicas Histológicas (11,7 e 58,7 ppbv), em decorrência da atividade desenvolvida nos locais. Na sala de Macroscopia, os níveis de formaldeído encontrados foram acima do limite (100 ppbv) estabelecido por órgãos internacionais que controlam a qualidade do ar em ambientes internos não industriais. As razões de mistura entre o ambiente interno e o ambiente externo, razões I/E, permitiram indicar a predominância dos compostos carbonílicos nos ambientes internos. A acroleína foi encontrada na faixa de 6,4 a 9,3 ppbv nos ambientes internos estudados. Na área externa, entretanto, foram encontrados valores similares (6,4 e 6,8 ppbv) aos dos ambientes internos obtendo razões I/E próximas de 1. Os compostos podem ter sido emitidos por materiais de construção e acabamento, fumaça do tabaco, adesivos, via metabolismo microbiano e bacteriano ou podem ter sido transportados por correntes de ar do ambiente externo para o ambiente interno / The quantification of 11 carbonyl compounds (formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, butiraldehyde, benzaldehyde, isovaleraldehyde, valeraldehyde and 2,5-dimethylbenzaldehyde) and the identification of another 43 volatile organic compounds (alkanes, alkenes, aromatic, halogenated and nitrogenated compounds) have been done with samples of 9 different indoor places inside the University Hospital at USP in São Paulo. Among the carbonyl compounds, there where found higher quantities of formaldehyde, acetone, acetaldehyde and acrolein in this order. The highest ratios of formaldehyde mixture have been observed at the Macroscopic room (169.88 and 90.2 ppbv) and Histological Techniques (11.7 and 58.7 ppbv), due to the routine activities of these places. At the Macroscopy room, the level of formaldehyde identified (100 ppbv) was above the international limits established to non-industrial internal places. The ratios of the mixture of indoor and outdoor places, I/O, indicate the biggest presence of carbonyl compounds in internal places. Acrolein has been identified (6.4 to 9.3 ppbv) at indoor places. At the external area, there where found similar values (6,4 to 6,8 ppbv), and the ratio I/O obtained is near to 1. The origin of these compounds is possibly construction materials, smoke of cigarettes, adhesives, metabolism of microorganisms or they may have come from the outdoor to the indoor

Les moisissures sont des biocontaminants courants des environnements intérieurs causant la biodégradation des matériaux qu'ils colonisent et favorisant l'apparition de diverses pathologies, notamment respiratoires telles que des allergies, des infections ou des toxi-infections.En raison de ces impacts, la maîtrise de la contamination fongique constitue une préoccupation majeure pour des secteurs aussi divers que les industries agro-alimentaires, pharmaceutiques, les hôpitaux ou encore les établissements patrimoniaux. Actuellement, les techniques utilisées pour surveiller ces environnements sensibles reposent sur la mesure de particules biologiques en suspension dans l'air émises après sporulation des moisissures. Afin de prévenir les effets de la prolifération de moisissures, le Centre Scientifique et Technique du Bâtiment (CSTB) a développé un indice de contamination fongique basé sur la détection de Composés Organiques Volatils (COV) spécifiques émis dès le début de cette croissance microbienne avant même l'émission dans l'air de particules délétères (Moularat, Robine et al. 2008; Moularat, Robine et al. 2008). Cet outil, breveté en 2007 (Moularat 2007), a été employé lors de différentes campagnes de mesures dans l'habitat, les bureaux, les écoles, les crèches, les musées…(Moularat, Derbez et al. 2008; Joblin, Moularat et al. 2010; Moularat, Hulin et al. 2011; Hulin, Moularat et al. 2012). Depuis le CSTB a élaboré un prototype de balise de surveillance intégrant cet indice et constitué de capteurs gaz à base de Polymères Conducteurs Electroniques (PCE), en collaboration avec l'ESIEE Paris (l'Ecole d'Ingénieurs de la Chambre de Commerce et d'Industrie de Paris) (pour la balise) et le Laboratoire de Physico-chimie des Polymères et des Interfaces (LPPI) (pour les PCE). Ainsi des capteurs à base de polypyrrole (PPy) et de Poly-(3,4-éthylènedioxythiophène)-poly(styrènesulfonate) (PEDOT-PSS) ont permis de différencier un environnement contaminé d'un environnement sain. Si ces couches sensibles se sont montrées efficaces pour la détection par l'identification d'une empreinte globale de COV d'origine fongique, elles ne s'avèrent pas encore suffisamment sélectives pour réaliser l'identification de chaque COV, indispensable pour le calcul de l'indice.Dans le cadre de la surveillance de la qualité microbiologique de l'air des environnements intérieurs, cette thèse a pour ambition de prolonger ces travaux en étudiant les mécanismes d'interaction entre COV et PCE en vue de l'application au développement de micro-capteurs chimiques adaptés à la mesure in situ. Cette recherche implique à la fois l'optimisation de la sensibilité et de la sélectivité de ces polymères et le développement d'une matrice de capteurs.Le premier aspect de cette étude a consisté à synthétiser de nouveaux PCE, plus spécifiques sur la base de ceux identifiés comme pertinents lors de la thèse de Joblin en 2011. Ainsi, des polymères, à base de pyrrole fonctionnalisés en position 1 et 3, ont été synthétisés par voie électrochimique. Le PEDOT-PSS, polymère commercial (sous forme de suspension dans l'eau), a, quant-à-lui, été conditionné par différents traitements thermiques.Le second aspect a porté sur l'étude de l'influence de l'exposition des COV à ces PCE sur leurs propriétés physico-chimiques. Ainsi, des caractérisations morphologiques, électrochimiques, optiques ainsi que la variation des propriétés de surface ont permis de mettre en évidence des interactions faibles, en général de type van der Waals ou par liaison hydrogène, entre COV et PCE.Enfin, le dernier aspect a porté sur l'étude expérimentale de la réponse des capteurs en contact avec différents COV issus ou non du métabolisme fongique. Cette dernière étape a permis de vérifier les hypothèses de mécanismes d'interaction. Par ailleurs, la spécificité de la matrice de capteurs vis-à-vis des composés fongiques a été démontrée. Cette matrice de capteurs a également permis d'obtenir des signatures spéci / Conducting polymers can be used as active materials of sensing devices that find application in different areas, such as quality control of products in industries such as food and beverage, cosmetics and solvents, in the monitoring of air quality for environmental and safety purposes, and as an auxiliary tool in the diagnosis of diseases. In spite of this, as a general rule, the details of the prevailing interactions of the volatile compounds and the polymer are not well understood. For this reason, we have focused the work of this thesis on the characterization of the interactions between vapors of volatile organic compounds and thin films of conducting polymers. These films, that were the active components of the sensors, were prepared atop of different geometry of interdigitated electrodes via electropolymerization, where several preparation parameters (such as doping agents nature and concentrations, monomer nature, thermal annealing) were observed to assure an homogeneous growth of the polymeric film. Several characterizations such as electrochemical studies, AFM observations and UV-VIS-NIR spectra studies were used to obtain detailed information about the interaction mechanisms between VOC and conducting polymers. We have also measured the contact angle of water, formamide and diiodomethane deposited on the surface of the polymeric films to evaluate surface free energy (and its acid-base and dispersive components). The selectivity and sensitivity of the polymeric sensors when exposed to different volatile organic compounds (VOCs) have shown to be dependent not only of the properties of the analyzed VOC but also on the nature of the counter-ion used to dope the polypyrrole film. As a final conclusion, we can say that as a result of this work it becomes possible to optimize the design of an arrangement of sensors such that both a better sensitivity and a better selectivity sensitivity to a given chemical environment can be achieved.

Les composés organiques volatiles (COVs) sont les polluants organiques atmosphériques les plus abondants. Parmi les différentes solutions pour combattre cette pollution, l'utilisation d'adsorbants moléculaires tels que les zéolithes semble être efficace. Cependant les synthèses classiques de zéolithes aboutissent généralement à des tailles de cristaux de l'ordre de plusieurs dizaines de micromètres. Les capacités et les cinétiques de piégeage, sensibles aux phénomènes de diffusion et de surface pourraient potentiellement être améliorées par l'utilisation de nanocristaux ou de produits zéolithiques hiérarchisés (micro/mésoporeux). Dans ce travail de thèse, nous avons synthétisé des zéolithes aluminosiliciques ou purement siliciques de type structural FAU, MFI et *BEA. Ces dernières sont synthétisées avec différentes morphologies et tailles de particules telles que les nanocristaux et les zéolithes hiérarchisées (nanofeuillets et/ou nanoéponges en utilisant des agents structurants bifonctionnels). Ces matériaux sont comparés aux zéolithes conventionnelles, afin d'étudier l'influence de la morphologie sur la cinétique et la capacité de piégeage de COVs. Les caractéristiques structurales et texturales des zéolithes synthétisées ont été étudiées par ORX, MEB, manométrie d'adsorption/désorption de diazote, ATG-ATD, RMN du solide. Enfin, la capacité d'adsorption d'une molécule modèle, le n-hexane, au sein de ces zéolithes a été étudiée par thermogravimétrie. Dans le cas des zéolithes de type MFI et *BEA, les zéolithes hiérarchisées ont montré une augmentation de la capacité de piégeage en n-hexane par rapport aux zéolithes conventionnelles. La capacité de piégeage en n-hexane a été multipliée par 7 dans le cas des nanoéponges de type *BEA et par 6 dans le cas des nanocristaux de type *BEA comparés aux microcristaux de type *BEA (693 mg/g vs 103 mg/g et 591 mg/g vs 103 mg/g, respectivement). / Volatile organic compounds (VOCs) are the most abundant organic pollutants. Among the various solutions to fight against this pollution, the use of molecular adsorbents appears as a potential alternative for the control of contamination. The porous materials have many advantages due to their low cost, their physical characteristics and their useful properties related to their structure and their large surface area. However, conventional synthesis of zeolites generally lead to micrometer size crystals. The capacity and the kinetics of adsorption that are sensitive to the diffusion and the surface phenomena could be potentially improved by the use of zeolite nanocrystals or hierarchical products (micro / mesoporous). These nanomaterials have high potential due to their small size and their exalted outer surface that promote access of pollutants and improve the adsorption capacity. ln the thesis work, we synthesized zeolites with different structural types such as FAU, MFI and *BEA. Each structure type was synthesized in different morphologies such as nanosponges and /or nanosheets using a bifunctional structuring agent, as well as nanocrystals by the clear solution method. These materials were compared with conventional micrometer-sized zeolites. The purity and the porous texture have been characterized by using XRD, SEM, nitrogen adsorption/desorption techniques, TGA-DTA and solid state NMR. Finally, the adsorption capacity of a model molecule, the n-hexane, in these zeolites have been studied by thermogravimetry. In the case of *BEA and MFI-type zeol ites, the hierarchical zeolites showed an increase of the adsorption capacity of n-hexane compared to conventional zeolites. The adsorption capacity of n-hexane was multiplied by 7 in the case of *BEA-type nanosponges and by 6 in the case of the *BEA-type nanocrystals compared to *BEA_type microcrystals (693 mg / g vs 103 mg / g and 591 mg / g vs 103 mg / g, respectively).