Les métaux lourds et les radionucléides sont présents dans différents écosystèmes du monde à cause de contaminations naturelles ou des activités anthropiques. L’utilisation de micro-organismes pour restaurer ces écosystèmes pollués, processus connu sous le nom de bioremédiation, suscite beaucoup d’intérêt, spécialement aux pH proches de la neutralité. Les minéraux de fer qui encroûtent les bactéries neutrophiles du fer, notamment les Oxydes de Fer Biogéniques (BIOS en anglais), ont une structure très faiblement cristalline, qui en plus de leur grande surface et réactivité font d’eux d’excellents supports pour le piégeage de polluants inorganiques. Dans cette thèse nous avons étudié les différents mécanismes de piégeage de l’uranium uranium par la bactérie neutrophile Sphaerotilus natans, choisie comme modèle bactérien de micro-organismes du fer capables de filamenter en formant des gaines. S. natans peut croître sous forme de cellules individuelles ou formant des filaments. Ces derniers ont été utilisés pour étudier la biosorption d’U(VI) et sa sorption sur les BIOS. De plus, la sorption d’U(VI) sur les analogues abiotiques de ces minéraux de fer a été testée. Afin d’utiliser les filaments de S. natans pour piéger l’U(VI), il était nécessaire d’identifier les facteurs induisant la filamentation de S. natans. L’influence de l’oxygène a été établie en utilisant des techniques de biologie moléculaire et nos résultats ont démontré que tandis qu’en condition d’oxygène saturé elle croît sous forme de cellules individuelles, une diminution modérée d’oxygène à ~ 3 mg O2.L-1 la fait croître sous la forme désirée, des filaments de S. natans.Les BIOS attachés aux filaments de S. natans ainsi que ses analogues abiotiques ont été analysés pas XAS au seuil K du Fe. Les deux matériaux identifiés sont des phosphates de fer(III) amorphes avec une faible proportion de fer(II), qui présentent une réactivité élevée pour le piégeage de polluants inorganiques. L’EXAFS au seuil LIII de l’U a montré la même structure pour les couches O, tandis que celles P, Fe et C étaient différentes en fonction des sorbants. Une étude intégrée qui combine des techniques expérimentales avec des calculs de spéciation a permis de décrire les isothermes d’adsorption de l’U(VI) en utilisant un modèle de complexation de surface. Ces résultats suggèrent que les groupes phosphoryles et carboxyles sont les groupes fonctionnels principaux pour la biosorption d’U(VI) par des filaments de S. natans. Les résultats de cette thèse vont aider à comprendre les processus contrôlant l’immobilisation de l’U(VI), soit par la biosorption sur S. natans, la sorption sur les BIOS ou la sorption sur les phosphates de fer, et en conséquence le devenir de l’U en conditions neutres / Heavy metals and radionuclides are present in some ecosystems worldwide due to natural contaminations or anthropogenic activities. The use of microorganisms to restore those polluted ecosystems, a process known as bioremediation, is of increasing interest, especially under near-neutral pH conditions. Iron minerals encrusting neutrophilic iron-related bacteria, especially Bacteriogenic Iron Oxides (BIOS), have a poorly crystalline structure, which in addition to their large surface area and reactivity make them excellent scavengers for inorganic pollutants. In this PhD work we studied the different mechanisms of uranium scavenging by the neutrophilic bacterium Sphaerotilus natans, chosen as a model bacterium for iron-related sheath-forming filamentous microorganisms. S. natans can grow as single cells and filaments. The latter were used to investigate U(VI) biosorption and U(VI) sorption onto BIOS. In addition, uranium sorption onto the abiotic analogues of such iron minerals was assessed. In order to use S. natans filaments for U(VI) scavenging, it was necessary to identify factors inducing S. natans filamentation. The influence of oxygen was ascertained by using molecular biology techniques and our results revealed that while saturated oxygen conditions resulted in single cell growth, a moderate oxygen depletion to ~ 3 mg O2.L-1 led to the desired filamentous growth of S. natans. BIOS attached to S. natans filaments as well as the abiotic analogues were analysed by XAS at Fe K-edge. Both materials were identified as amorphous iron(III) phosphates with a small component of Fe(II), with a high reactivity towards scavenging of inorganic pollutants. In addition, EXAFS at the U LIII-edge revealed a common structure for the O shells, while those for P, Fe and C were different for each sorbent. An integrated approach combining experimental techniques and speciation calculations made it possible to describe U(VI) adsorption isotherms by using a surface complexation model. These results suggested the role of phosphoryl and carboxyl groups as the main functional groups involved in the U(VI) biosorption by S. natans. The results of this PhD work will help to better understand the processes governing U(VI) immobilization, either by S. natans biosorption, sorption onto BIOS or sorption onto iron phosphates, an thus the fate of uranium in near-neutral pH environments

Fluoride in drinking water can lead to a crippling disease called fluorosis. As there is no cure for fluorosis, prevention is the only means of controlling the disease and research into fluoride remediation is critical. This work begins by providing a new approach to assessing fluoride remediation strategies using a combination of groundwater chemistry, saturation indices, and multivariate statistics based on the results of a large groundwater survey performed in a fluoride-contaminated region of India. From the Indian groundwater study, it was noted that one technique recommended for defluoridation involved using hydrous ferric oxide (HFO) as a solid phase sorbent for fluoride. This prompted investigation of bacteriogenic iron oxides (BIOS), a biogenic form of HFO, as a means of approaching bioremediation of fluoride. Batch sorption experiments at ionic strengths ranging from 0.001 to 0.1 M KNO3 and time course kinetic studies with BIOS and synthetic HFO were conducted to ascertain total sorption capacities (ST), sorption constants (Ks), and orders of reaction (n), as well as forward (kf) and reverse (kr) rate constants. Microcosm titration experiments were also conducted with BIOS and HFO in natural spring water from a groundwater discharge zone to evaluate fluoride sorption under field conditions. This thesis contributes significant, new information regarding the interaction between fluoride and BIOS, advancing knowledge of fluoride remediation and covering new ground in the uncharted field of fluoride bioremediation.

Fluoride in drinking water can lead to a crippling disease called fluorosis. As there is no cure for fluorosis, prevention is the only means of controlling the disease and research into fluoride remediation is critical. This work begins by providing a new approach to assessing fluoride remediation strategies using a combination of groundwater chemistry, saturation indices, and multivariate statistics based on the results of a large groundwater survey performed in a fluoride-contaminated region of India. From the Indian groundwater study, it was noted that one technique recommended for defluoridation involved using hydrous ferric oxide (HFO) as a solid phase sorbent for fluoride. This prompted investigation of bacteriogenic iron oxides (BIOS), a biogenic form of HFO, as a means of approaching bioremediation of fluoride. Batch sorption experiments at ionic strengths ranging from 0.001 to 0.1 M KNO3 and time course kinetic studies with BIOS and synthetic HFO were conducted to ascertain total sorption capacities (ST), sorption constants (Ks), and orders of reaction (n), as well as forward (kf) and reverse (kr) rate constants. Microcosm titration experiments were also conducted with BIOS and HFO in natural spring water from a groundwater discharge zone to evaluate fluoride sorption under field conditions. This thesis contributes significant, new information regarding the interaction between fluoride and BIOS, advancing knowledge of fluoride remediation and covering new ground in the uncharted field of fluoride bioremediation.