No presente trabalho foi avaliado o potencial do reator anaeróbio de leito fixo-estruturado e fluxo descendente (down-flow fixed strucutured bed reactor – DFSBR) para o tratamento de drenagens ácidas de minas (DAM) com vistas à recuperação de metais. Vinhaça de cana-de-açúcar foi utilizada como doador de elétrons para bactérias redutoras de sulfato (BRS) e ferro (Fe2+) foi adicionado como metal de referência. Em associação com a sulfetogênese, produção de metano foi promovida pela relação DQO/SO42- de 2,0, maior que a relação estequiométrica de oxidação da matéria orgânica via redução de SO42- (0,67). Concentrações afluentes de DQO e SO42- da ordem de 4000 mg.L-1 e 2000 mg.L-1, respectivamente, foram mantidas durante todo o período experimental (547 dias), sendo o reator operado com TDH de 20 h. Durante a ETAPA 1 (277 dias) o DFSBR foi alimentado com substrato sintético simulando a fração solúvel da vinhaça e recebeu cargas crescentes de ferro (0,07 a 0,51 g Fe2+.L-1.d-1) para avaliação do potencial de remoção de metais. Foram obtidas eficiências de remoção de DQO e SO42- de 94±2% e 97±3%, respectivamente. Remoção de ferro de 95±5% foi alcançada, assim como proporções crescentes de ferro (de até 55%) nas cinzas do precipitado. Ao longo da ETAPA 2 (100 dias) vinhaça foi utilizada como único doador de elétrons e diferentes razões de recirculação foram estudadas (0, 50, 100 e 150 vezes), com velocidades superficiais do escoamento variando de 0,03 a 5,20 m.h-1. A eficiência de remoção de DQO de 82±6% foi atribuída à presença de compostos recalcitrantes na vinhaça, ao passo que a remoção de SO42- permaneceu próxima da alcançada na ETAPA 1 (95±5%). Uma produção volumétrica de metano da ordem de 390 mL CH4.L-1.d-1 foi obtida (CNTP). A despeito da variação nas taxas de reciclo, maior estabilidade e eficiência de remoção de ferro (96±3%) foram determinadas na ausência de recirculação, com ganhos econômicos para o processo. Durante a ETAPA 3 (170 dias) a diminuição gradativa do pH afluente de 6,30 para 3,50 foi realizada. Apesar da supressão de alcalinidade, o sistema atingiu eficiências de remoção de SO42- de 97±1% e remoção de ferro de 95±4%. Foram observados efeitos adversos sobre o metabolismo metanogênico, com queda na produção de metano de 380 para 230 mL CH4.L-1.d-1, acompanhada por aumento da DQO residual no efluente (1500 mg DQO.L-1). Ainda assim, o DSFBR foi capaz de elevar o pH da água residuária de 3,5 para 6,9, confirmando o potencial do sistema para a neutralização de DAM. A caracterização da comunidade microbiana por análise do sequenciamento do gene RNAr 16S indicou predominância dos gêneros Desulfovibrio e Methanosaeta, comprovando o estabelecimento simultâneo dos processos sulfetogênicos e metanogênicos. Por fim, os resultados apontaram perspectivas promissoras de aplicação do DFSBR ao tratamento de DAM via redução de SO42- favorecendo a precipitação e separação de metais em reator de único estágio. A vinhaça de cana-de-açúcar também se mostrou um adequado doador de elétrons para o processo. / This work evaluated the potential of the down-flow fixed-structured bed anaerobic reactor (DFSBR) for the treatment of acid mine drainage (AMD) aiming at metals recovery. Sugarcane vinasse was used as electron donor for sulfate-reducing bacteria (BRS) and iron (Fe2+) was added as reference metal. In association with sulfidogenesis, methane production was promoted by the applied COD/SO42- ratio of 2.0, which is higher than the stoichiometric ratio for organic matter oxidation solely by SO42- reduction (0.67). Affluent concentrations of COD and SO42- were kept close to 4000 mg.L-1 and 2000 mg.L-1, respectively, over the entire experimental time (547 days). The reactor was operated with HRT of 20 h. During STAGE 1 (277 days) the DFSBR was fed with synthetic substrate simulating the soluble fraction of vinasse and received increasing iron loads (0.07 to 0.51 g Fe2+.L-1.d-1) to verify the potential for metal removal. COD and SO42- removal efficiencies were 94±2% and 97±3%, respectively. Iron removal of 95±5% was achieved, as well as increasing proportions of iron (up to 55%) were observed in the ashes of precipitate. Throughout STAGE 2 (100 days) sugarcane vinasse was used as unique electron donor whereas different recirculation ratios were studied (0, 50, 100 and 150 times), with superficial flow velocities ranging from 0.03 to 5.20 m-1. COD removal efficiency of 82±6% was attributed to the presence of recalcitrant compounds in the vinasse, while the removal of SO42- remained close to that previously achieved during STAGE 1 (95±5%). Volumetric methane production near of 390 mL CH4.L-1.d-1 was obtained (STP). Although the variation in the recycle rates, greater stability and efficiency of iron removal (96±3%) were determined in the absence of recirculation, with economic gains for the process. During the STAGE 3 (170 days) gradual decrease of the pH affluent from 6.30 to 3.50 was performed. Despite the alkalinity suppression, the system achieved SO42- removal efficiencies of 97±1% and iron removal close to 95±4%. Adverse effects over methanogenic metabolism were observed once methane production decreased from 380 to 230 mL CH4.L-1.d-1, which was followed by a residual COD increase in the effluent (1500 mg COD.L-1). Nevertheless, the DSFBR was able to raise the pH of the wastewater from 3.5 to 6.9, indicating the potential of such system for AMD neutralization. 16S rRNA gene sequencing analysis for microbial community characterization showed predominance of the genera Desulfovibrio and Methanosaeta, confirming the simultaneous establishment of sulfidogenic and methanogenic processes. Finally, the results presented promising perspectives for the DFSBR application to the AMD treatment via SO42- reduction, also favoring metals precipitation and separation in a single-stage reactor. Sugarcane vinasse was also considered a suitable electron donor for the process.

La formation de méthylmercure, la forme la plus toxique du mercure, est due à l’activité bactérienne anaérobie. Afin de connaître la contribution des compartiments microbiens (biofilms, eaux brutes, sédiments) dans la méthylation du mercure, nous avons évalué les vitesses de méthylation d’échantillons de mares de région tempérée (Lorraine) et subarctique (Québec, Canada). Si les bactéries des biofilms ne semblent pas plus méthylantes que d’autres, le sédiment apparait comme le compartiment le plus méthylant en lien avec la concentration en nutriments ainsi qu’avec la température. Ainsi, les changements climatiques actuels, en augmentant la température de l’eau et en favorisant l’activité biologique, peuvent faire de ces mares des sites préférentiels de la méthylation du mercure en milieu subarctique. Enfin, l’activité des biofilms a mené à la formation de rouille verte, un minéral capable de réduire HgII en mercure élémentaire, concurrençant ainsi la méthylation bactérienne / Monomethylmercury formation, the neurotoxic form of mercury, is mainly linked to anaerobic microbial activity. In order to assess the relative contribution of several microbial compartments (biofilms, raw water and sediment) we evaluated methylation of samples from ponds of temperate area (Lorraine, France) and from subarctic ponds (Nunavik, Quebec). Biofilms were not found to specifically promote mercury methylation, whereas sediment emerges as the main compartment involved in mercury methylation. The formation of methylmercury is positively linked to the temperature and to nutrients. Thus, by increasing the open water period, the water temperature and of the microbial activity, current climate changes may turn these ponds in preferential location for mercury methylation in the subarctic ecosystem. Finally, the reactivity of green rust, a mineral which can be produced by bacterial activity of environmental biofilms, may compete with mercury methylation by reducing HgII into Hg0

Reconnu par leur effet toxique, inhibiteur et corrosif, les sulfures (S2-, SH-, SH2) sont un sous-produit indésirable de la digestion anaérobie des boues de station de traitement des eaux domestiques de la ville de Marrakech, Maroc (STEP). Ils proviennent essentiellement de la réduction "dissimilatrice" des composés soufrés (SO4 2-, SO3 2-, S2O4 2- ..) contenus dans ces boues. Ce processus est réalisé par un groupe bactérien anaérobie appelé bactéries sulfatoréductrices (BSR). Une fois dans le biogaz, les sulfures sous forme gazeuse réduisent en plus la durée de vie des installations et des équipements de la STEP. Elle est ainsi dotée d’installations biologiques et physico-chimiques lui permettant d’éliminer ces sulfures avant la transformation du biogaz en énergie électrique. Cependant, ces procédés sont onéreuses et grandes consommatrices d’énergies. D’où l’idée de minimiser la production des sulfures au sein même des digesteurs anaérobies. Pour cela, il était nécessaire d’abord de connaître les microorganismes à l'origine de la production des sulfures (BSR), ceux potentiellement impliqués dans leur élimination (bactéries sulfo-oxydantes), et d’un groupe de microorganismes fermentaires (Synergistetes) intervenant dans le bon fonctionnement de la digestion anaérobie. Ces études ont été menées à la fois sur des d'approches moléculaires et culturales. Les résultats obtenus, ont permis de comprendre comment ces groupes bactériens, d’intérêts écologique et économique importants, interviennent dans la digestion anaérobie des boues de la STEP permettant à la fois d’accélérer les processus d’oxydation de la matière organique combinée à la réduction des composés soufrés et de minimiser la concentration des en sulfure dans le biogaz. / Recognized by their toxic, inhibitory and corrosive effect, sulfides (S2-, SH-, H2S) are an undesirable by-product of the anaerobic digestion of from domestic wastewater treatment plants sludge in the city of Marrakech, Morocco (WWTP). They produced mainly by the dissimilatory reduction of sulfur compounds (SO42-, SO32-, S2O42-) contained in these sludges. This process is performed by an anaerobic bacterial group called sulfate reducing bacteria (SRB). Once in the biogas, the sulfides in gaseous form shorten in addition the lifetime of the installations and equipments of the WWTP. It is thus equipped with biological and physicochemical installations allowing it to eliminate these sulfides before the transformation of biogas into electrical energy. However, these processes are expensive and consume large amounts of energy. Hence the idea of minimizing the production of sulfides within anaerobic digesters. For this, it was first necessary to know the microorganisms originating of the production of sulfides (SRB), those potentially involved in their elimination (sulfur oxidizing bacteria), and a group of fermentative microorganisms (Synergistetes) involved in the good functioning of the anaerobic digestion. These studies were conducted on both molecular and cultural approaches. The results obtained allowed to understand how these bacterial groups, of great ecological and economic interest, are involved in the anaerobic digestion of sludge from the WWTP, which both accelerates the oxidation processes of the organic matter combined with the reduction of sulfur compounds and to minimize the concentration of sulfide in biogas.

Ubiquitaires et très anciens, les communautés des tapis microbiens font preuve de capacités métaboliques et adaptatives très importantes. Situés en zone côtières, ces écosystèmes peuvent être soumis à des contaminations pétrolières. Dans ce contexte, cette étude vise d’une part à décrire la structure et le fonctionnement de tapis microbiens et d’autre part à comprendre l’impact d’une contamination pétrolière sur ces écosystèmes. Cette étude porte sur deux tapis microbiens de l’étang de Berre aux paramètres physico-Chimiques proches mais présentant des contaminations pétrolières contrastées. Le fonctionnement du système étant tributaire d’autres facteurs tels que la lumière et les saisons, les variations saisonnières et nycthémérales ont été prises en compte dans cette étude. Un accent particulier a également été porté sur le cycle du soufre de par son importance en milieu marin. Les résultats de cette étude mettent en évidence des structures de communautés différentes entre les deux tapis au niveau global, la séparation spatiale prévalant sur la séparation saisonnière. La fraction active de la communauté du site contaminé présente une évolution linéaire tandis que celle du site témoins suit pour sa part les variations saisonnières. Au niveau du site contaminé une augmentation de l’expression des gènes impliqués dans la dégradation des hydrocarbures couplée à une biodégradation des hydrocarbures suggère que le tapis contaminé est adapté à la contamination pétrolière. Malgré les différences de structures et d’activités de dégradation, des profils métaboliques très semblables sont cependant observables entre les deux tapis, avec des fonctions similaires laissant supposer une redondance fonctionnelle. Des variations saisonnières et nycthémérales ont également été observées avec notamment des Desulfobulbaceae plus abondantes au printemps et plus actives en journée. Des études culturales ont été réalisées en parallèle. Elles permettront d’appréhender de manière complémentaire la dynamique des communautés des sulfato-Réducteurs au sein du tapis et de mieux comprendre les variations mises en évidence dans cette étude. / Ubiquist and very ancient, the microbial mats communities demonstrate very important metabolic and adaptive capacities. Located in the coastal area, these ecosystems may be subject to oil contamination. In this context, the aim of this study is on one hand to describe the structure and functioning of microbial mats and on the other to understand the impact of oil contamination on these ecosystems. This study focused on two microbial mats from the Berre lagoon with close physical chemical parameters but with contrasted hydrocarbon contamination levels. The functioning of the system is dependent on other factors such as light and seasons, diurnal and seasonal variations were taken into account in this study. Special emphasis was placed on the sulfur cycle due to its importance in the marine environments. The results of this study highlighted different communities’ structures at the global level between both mats, the spatial variation prevailed on seasonal variation. The active part of the community from the contaminated site shows a linear trend while that one of the uncontaminated site follows the seasonal variations. The contaminated site shows genes involved in hydrocarbon degradation more expressed coupled to a hydrocarbon biodegradation suggesting that the contaminated mat is adapted to the petroleum contamination. Despite these differences in the structure and the degradation capacities, very similar metabolic profiles are observed between the two mats with similar functions, suggesting functional redundancy. Seasonal and diurnal variation was also observed, the Desulfobulbaceae were particularly more abundant in spring and more active during the day. A complementary cultural approach will allow to better understanding the dynamics of sulfate-Reducers communities in the mat and comprehending these variations.

Solid wastes containing sulfate, such as construction and demolition debris (CDD), are an important source of pollution, which can create a lot of environmental problems. It is suggested that these wastes have to be separated from other wastes, especially organic waste, and place it in a specific area of the landfill. This results in the rapid rise of the disposal costs of these gypsum wastes. Although these wastes can be reused as soil amendment or to make building materials, a concern has been raised by regulators regarding the chemical characteristics of the material and the potential risks to human health and the environment due to CDD containing heavy metals and a high sulfate content. Soils containing gypsum, namely gypsiferous soils, also have several problems during agricultural development such as low water retention capacity, shallow depth to a hardpan and vertical crusting. In some mining areas, gypsiferous soil problems occur, coupled with acid mine drainage (AMD) problems which cause a significant environmental threat. Reduction of the sulfate content of these wastes and soils is an option to overcome the above mentioned problems. This study aimed to develop sulfate removal systems to reduce the sulfate content of CDD and gypsiferous soils in order to decrease the amount of solid wastes as well as to improve the quality of wastes and soils for recycling purposes or agricultural applications. The treatment concept leaches the gypsum contained in the CDD by water in a leaching step. The sulfate containing leachate is further treated in biotic or abiotic systems. Biological sulfate reduction systems used in this research were the Upflow Anaerobic Sludge Blanket (UASB) reactor, Inverse Fluidized Bed (IFB) Reactor and Gas Lift Anaerobic Membrane Bioreactor (GL-AnMBR). The highest sulfate removal efficiency achieved from these three systems ranges from 75 to 95%. The treated water from the bioreactor can then be reused in the leaching column. Chemical sulfate removal (abiotic system) is an alternative option to treat the CDD leachate. Several chemicals were tested including barium chloride, lead(II) nitrate, calcium chloride, calcium carbonate, calcium oxide, aluminium oxide and iron oxide coated sand. A sulfate removal efficiency of 99.9% was achieved with barium chloride and lead(II) nitrate.For AMD and gypsiferous soils treatment, five types of organic substrate including bamboo chips (BC), municipal wastewater treatment sludge (MWTS), rice husk (RH), coconut husk chip (CHC) and pig farm wastewater treatment sludge (PWTS) were tested as electron donors for biological sulfate reduction treating AMD. The highest sulfate reduction efficiency (84%) was achieved when using the combination of PWTS, RH and CHC as electron donors. Then, this organic mixture was further used for treatment of the gypsiferous soils. The gypsum mine soil (overburden) was mixed with an organic mixture in different amounts including 10, 20, 30 and 40% of soil. The highest sulfate removal efficiency of 59% was achieved in the soil mixture which contained 40% organic material.The removal of sulfide from the effluent of the biological sulfate reduction process is required as sulfide can cause several environmental impacts or be re-oxidized to sulfate if directly discharged to the environment. Electrochemical treatment is one of the alternatives for sulfur recovery from aqueous sulfide. A non-catalyzed graphite electrode was tested as electrode for the electrochemical sulfide oxidation. A high surface area of the graphite electrode is required in order to have less internal resistance as much as possible. The highest sulfide oxidation rate was achieved when using the external resistance at 30 Ω at a sulfide concentration of 250 mg L-1

Les effondrements miniers en Lorraine (France) ont pour origine la rupture des piliers de soutien constitués de minerai de fer. Leur rupture n'est pas seulement due aux seules contraintes mécaniques qu’exerce le recouvrement mais également aux différentes transformations minéralogiques du minerai de fer, compromettant sa cohésion et sa résistance et par conséquent, la stabilité des piliers. On parle alors d’altération/vieillissement minéralogique du minerai de fer. Les mécanismes chimiques qui entrainent ces transformations minéralogiques sont désormais bien connus mais l’influence de l’activité bactérienne n’est pas encore bien comprise. Des travaux préliminaires ayant soulevé le rôle possible des activités microbiennes, ce travail de thèse s'est alors appliqué à identifier les métabolismes bactériens susceptibles de réagir avec le minerai de fer en conditions aérobie et anaérobie, et à en caractériser les effets physico-chimiques, minéralogiques et mécaniques. Les groupes métaboliques bactériens suspectés d’être impliqués dans ces réactions (activités ferri-réductrices, ferro-oxydantes et sulfato-réductrices) ont été identifiés dans les eaux de mine et incubés en présence du minerai de fer, en souche pure ou avec un consortium issu de l’eau de mine. Les bactéries ferri-réductrices (IRB), sulfato-réductrices (BSR) et acidophiles ferro-oxydantes ont été les seules qui, dans les conditions de laboratoire, ont impacté significativement le minerai en modifiant le ratio Fe(II)/Fe(III). Une phase ferro-carbonatée et de la pyrite se sont formées respectivement au cours des incubations avec les IRB et BSR, et ont été caractérisées par analyse du solide (spectroscopies infrarouge en réflexion diffuse (DRIFTS) et Mössbauer et par diffraction aux rayons X). Des bactéries nitrate-réductrices ont aussi été testées et aucune modification significative du ratio Fe(II)/Fe(III) du minerai de fer n’a été observée. Enfin, les propriétés mécaniques du minerai de fer ont été mesurées après les réactions d’oxydo-réduction biologiques et purement chimiques. Des modifications sensibles de ces propriétés mécaniques par rapport à l’état initial ont ainsi pu être mises en évidence. Sur la base de ces résultats, l’hypothèse de l’altération mécanique du minerai de fer par des activités microbiennes est donc tout à fait réaliste. / Mine collapses occurred in Lorraine (France) because of the failure of safety pillars made of iron ore. Their failure is not only due to the mechanic stresses applied by the overburden, but also due to the various mineralogical transformations in iron ore which decrease material cohesion and resistance and thus stability of pillars. This is called mineralogical alteration/ageing of iron ore. Chemical mechanisms inducing these mineralogical transformations are now well known but the influence of microbial activity is not well understood yet. Preliminary works have raised the possible role of microbial activity, then the focus of this work was to identify the various bacterial metabolisms capable of reacting with iron ore and to characterize the physico-chemical, mineralogical and mechanical effects. The bacterial metabolism groups possibly implied in these reactions (iron-reducing (IRB), iron-oxidizing and sulfate-reducing bacteria (SRB)) were identified from the mine water. As pure strain or as consortium, these bacteria were incubated with iron ore. Under laboratory conditions, only iron-reducing, sulfate-reducing and acidophilic iron-oxidizing bacteria impacted iron ore samples by modifying the Fe(II)/Fe(III) ratio. A ferrous-carbonate phase and pyrite were formed during incubations with IRB and SRB, respectively. These minerals were characterized from analysis of the solid phase (Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Mössbauer spectroscopy and X-ray diffraction). The impact nitrate-reducing bacteria was also tested but the Fe(II)/Fe(III) ratio of iron ore was not modified significantly. Finally, mechanical properties of iron ore were measured after microbial and purely chemical redox reactions. Discernible modifications of these mechanical properties were observed. From these results, the alteration of iron ore mechanical properties by bacterial activities is a realistic assumption.

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