Fungi play important geoactive roles in the biosphere, particularly element biotransformations and biogeochemical cycling, metal and mineral transformations, decomposition, bioweathering, and soil and sediment formation. Fungi can apply various mechanisms to effect changes in metal speciation, toxicity and mobility, mineral formation and/or mineral dissolution. This research has examined fungal roles in bioweathering and bioleaching of zinc sulfide ore, together with an investigation of the role of fungal phosphatases in the bioprecipitation of uranium and lead when utilising an organic phosphorus-containing substrate as the sole phosphorus source. The results obtained revealed that test fungal species showed bioweathering effects on zinc sulfide ore, and clear evidence of biotransformation and bioleaching of zinc sulfide was obtained after growth of A. niger. The formation of zinc oxalate dihydrate resulted from oxalic acid excretion. The formation of uranium- and lead-containing biominerals after growth of yeasts and filamentous fungi with organic phosphorus sources have also been demonstrated and characterized. Test fungi were capable of precipitating uranium phosphate and pyromorphite, and also produced mycogenic lead oxalate during this process. This work is the first demonstration that filamentous fungi are capable of precipitating a variety of uranium- and lead-containing phosphate biominerals when grown with an organic phosphorus source. The role of fungal processes in the bioweathing and bioleaching of mineral ores, and the significance of phosphatases in the formation of uranium and lead secondary minerals has thrown further light on potential fungal roles in metal and mineral biogeochemistry as well as the possible significance of these mechanisms for element biorecovery or bioremediation.

Le crassier du site MetalEurop (Noyelles-Godault) a accueilli des scories de première fusion entre les années 1936 à 2003. Il est actuellement constitué de 4 millions de tonnes de ces matériaux générés par les deux procédés pyrométallurgiques les plus usités dans le monde pour la production du plomb et du zinc : le procédé Lead Blast Furnace (LBF) et le procédé Impérial Smelting Furnace (ISF). L'utilisation de ces scories en tant que matériau de substitution dans les ciments et dans les routes a été envisagée et a fait l'objet de recherches, mais présente des risques environnementaux, c'est-à-dire, essentiellement la dissémination de polluants (Pb et Zn) / Primary smelting slags, known as Lead Blast Furnace (LBF) and Imperial Smelting Furnace (ISF), were generated by the former pyrometallurgical industries located in Noyelles-Godault, Northern France. Following its closure in 2003, 4 million tons of primary slags have been landfilled as a heap in the vicinity of the Deûle River, near the industrial basin of Nord-Pas-de-Calais. These slag materials are often enriched in particular metals (Pb, Zn) that can be released into the environment through alteration processes and leaching. Many biological and chemical processes might take place within these tailings and thus affect significantly the slag weathering. Predicting the environmental impact of these wastes requires an understanding of the mineral-water interactions as well as the influence of the biological activities (the involvement of microorganisms). Thus, this research is designed to simulate the natural weathering of slag by simulating different weathering conditions with or without the involvement of the microorganisms as well as by varying several chemical parameters. Chemical weathering of both LBF and ISF slags was studied by as a function of pHs (4, 5.5, 7, 8.5 and 10) as well as under two atmospheres (open air and nitrogen). Significant amounts of Ca, Fe and Zn were released under acidic conditions (pH 4) with a decrease towards the neutral to alkaline conditions (pH 7 and 10) for both slags. The concentrations of all elements increased gradually after 216 h compared to initial 24 h of leaching period. The presence of oxygen under open-air atmosphere not only enhanced oxidative weathering but also encouraged formation of secondary oxide and carbonate phases. In addition, Zn dissolution was related to extremes zinc isotopic signatures in the leachate; heavier δ66Zn values at low pH than at high pH for both slags under open-air atmosphere. On the other hand, bioweathering of both slags was studied in the presence of a pure heterotrophic bacterial strain (Pseudomonas aeruginosa) in a bioreactor operated in batch conditon as well as in a semi-flow through reactor with intermittent leachate renewal conditions. P. aeruginosa is shown to play a significant role in slags weathering by enhancing the leaching and solubility of Zn and Pb. In addition, the cumulative bulk release of dissolved Fe, Si, Ca and Mg doubled in the presence of bacteria, probably due to the release of soluble complexing organic molecules (e.g. siderophores). Bacterial biomass served as the bioadsorbent for Pb, Fe and Zn as 70-80% of Pb and Fe, 40-60% of Zn released are attached to and immobilized by the bacterial biomass. Oxides, hydroxides and carbonates were predicted as secondary phases during chemical weathering of slags whereas carbonates and phosphates were dominant phases during bioweathering. These predictions were in agreement with the observations by Scanning Electron Microscopy (SEM) with Energy Dispersive X-Ray Analysis (EDS), Transmission Electron Microscopy (TEM) analysis, and X-ray Photoelectron Spectroscopy (XPS) analysis

Dans un premier temps, nous avons synthétisé et caractérisé une chondrite à enstatite reconstituée. En étudiant cet objet, nous avons pu identifier et comprendre le signal Raman des sulfures présents dans les météorites à enstatite. La réponse Raman de ces phases est obtenue via l'activation des modes infra-rouge suite à une modification de la symétrie dans le réseau cristallin. Dans un second temps, nous avons utilise cet analogue pour comprendre le processus de bio-alteration des chondrites à enstatite dans les conditions terrestres actuelles, donc en aérobiose. Afin de bien comprendre ce phénomène de bio altération sur ce matériau complexe, il a été indispensable d'étudier ce mécanisme sur chacune des phases présentes dans celui-ci. Ainsi l'analogue de chondrite à enstatite, l'enstatite, la troilite, l'alliage Fe-Si et aussi de l'olivine ont été altérés abiotiquement et bio altérés par les souches Acidithiobacillus ferrooxidans et Acidithiobacillus thiooxidans, ¨¤ pH ¡Ö 2 ¨¤ T = 20¡ãC. Cette étude a permis d'obtenir et d'interpréter à l'échelle de la microscopie électronique à balayage les principales phases et microstructures qui se développent lors de l'altération abiotique ou biologique d'une chondrite à enstatite. En parallèle, des mesures régulières de la chimie du milieu aqueux ont permis d'étudier la cinétique de lixiviation de ces expériences de bio-alteration et de la comparer à une modélisation thermodynamique et cinétique, que nous avons effectué avec le programme Jchess. Nos résultats montrent qu'en opposition avec ce qui a été observe sur les phases séparées, les cinétiques de dissolution sont très différentes lorsque les différentes phases sont associées dans l'analogue de chondrite à enstatite : la troilite se dissout bien plus lentement que dans les expériences sur phases séparées alors que l'enstatite se dissout plus vite. La dissolution plus lente de la troilite est attribuée à la présence de monosulfures très solubles dans le matériau de départ. Ces observations pourront être utilisées pour modéliser et interpréter l'évolution d'une chondrite à enstatite à la surface de la Terre et, au delà, de matériaux réduits associant métaux, sulfures et silicates. Les chondrites à enstatite constituent un substrat approprié pour les deux souches bactériennes étudiées qui, en présence de cet assemblage minéral, ont montré de l'activité biologique, en particulier la formation de biofilms, et ont accéléré les vitesses de dissolution / The aim of this study is to investigate the mineralogical and chemical processes which take place during the bioweathering of an enstatite chondrite by bacteria. Synthetic enstatite chondrites were made in laboratory in order to begin this complex study with simplified and well-defined materials. These analogs were shown to contain the major phases of enstatite chondrites: enstatite, Si-rich kamacite, troilite and unusual sulfides such as oldhamite or niningerite. First, the Raman study of this analog allowed to identify and understand the specific Raman signal of sulphides present in enstatite meteorites. The Raman signal of these phases is explained by infrared activation due to a symmetry modification in the crystal lattice. Then, in order to better understand the aqueous alteration of enstatite chondrites, each major phase and olivine were separately submitted to aqueous and aerobic alteration with or without Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans at pH ¡Ö 2 ¨¤ T = 20¡ãC. All experiments were characterized before and after alteration using scanning electron microscopy. Regular measurements og the chemistry of the aqueous medium were used to study the kinetics of leaching experiments of bio-alteration and compared to thermodynamic and kinetic modeling with JChess. Our results show that contrary to the observations on the separate phases, the dissolution kinetics are very different when the whole phases are associated in the enstatite chondrite analogue: troilite dissolves more slowly than in experiments on separate phases while enstatite dissolves faster. The slower dissolution of troilite is ascribed to the presence of oldhamite and niningerite in the starting material. These observations will be useful to understand and model the evolution of enstatite chondrites at the surface of the Earth and, beyond that, of reduced assemblages containing metals, sulphides and silicates. Enstatite chondrites are shown to be an appropriate substrate for the two bacterial strains which have shown biological activity, especially by the formation of biofilms and which have accelerated the dissolution kinetics

L’altération des roches silicatées constitue le dénominateur commun d’une multitude de problématiques environnementales et sociétales. Du fait de la difficulté d’extrapoler au milieu naturel les cinétiques de dissolution des minéraux mesurées in vitro, cette thèse propose de réviser en profondeur l’approche actuelle de la réactivité minérale du laboratoire au terrain. Ce travail démontre que l’évolution intrinsèque des propriétés texturales et structurales de l’interface réactive au cours de la dissolution induit des variations de vitesse qui ne peuvent être expliquées dans le cadre des théories thermocinétiques classiques. Nous proposons une nouvelle méthode permettant de sonder la réactivité biogéochimique des minéraux sur le terrain et de révéler les interactions réciproques entre le minéral et le monde microbien au sein de la minéralosphère. Nous démontrons la pertinence des phénomènes de passivation pour l’altération de surface et l’incapacité des microorganismes à les surmonter. / Chemical weathering of silicate minerals is central to numerous environmental and societal challenges. This study addresses the long-standing question of the inconsistency between field and laboratory estimates of dissolution kinetics, by revisiting current approaches of mineral reactivity. It is demonstrated that evolution of feldspar reaction rates are inaccurately describedby current kinetics rate laws, due to textural and structural changes occurring at the fluid-mineral interface over the course of the dissolution process. A novel method is developed to enable probing biogeochemical weathering rates in the field. Bacterial and fungal metagenomic data reveal that subtle reciprocal relationships are established between microorganisms and mineral substrates within the mineralosphere. This thesis emphasizes the impact of passivation phenomena on dissolution rates, under field-relevant reacting conditions and the incapacity of microorganisms to overcome the passivation barrier.