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De nos jours, la contamination des sols par les polluants organiques et inorganiques est une problématique majeure. Des techniques douces de remédiation, reposant sur l’utilisation de plantes et de microorganismes, associés à des amendements ou non, sont étudiées pour gérer ces sols. Parmi les différents amendements, le biochar est présenté dans la littérature comme pouvant répondre à ces attentes. Ce travail se propose d’évaluer l’impact des paramètres de pyrolyse sur les caractéristiques de huit biochars élaborés à partir de Miscanthus x giganteus, cultivé sur un sol contaminé en métaux, et de sélectionner le(s) biochar(s) susceptible(s) d’être le(s) plus performant(s) en termes de remédiation de sols contaminés en métaux (Cd, Pb, Zn) et/ou HAP. Il a été mis en évidence une forte influence de la température de pyrolyse sur les caractéristiques des biochars. De plus, les biochars ont présenté de fortes capacités de sorption des trois métaux et des HAP en solution, notamment pour les biochars produits à 600°C. Des expérimentations réalisées avec un sol artificiel et une terre agricole contaminés artificiellement ont mis en évidence la capacité de certains biochars à diminuer la disponibilité environnementale, la biodisponibilité et la bioaccessibilité orale des métaux et des HAP. Sur la base des résultats obtenus, un biochar a été sélectionné comme répondant le mieux aux attentes en termes de gestion de sols multicontaminés. Compte tenu des modifications structurelles du biochar dans les sols, il conviendrait de valider ces résultats sur le long terme, en condition in situ, tout en s’assurant de l’innocuité du biochar étudié et en intégrant les aspects socio-économiques. / Nowadays, soil contamination by the organic and inorganic pollutants represent a major issue. Gentle remediation options, comprising plants and microorganisms, and linked with the use of amendments or not, are implemented to manage these soils. Among the different amendments, the biochar is presented in the literature as being able to meet these expectations. This study aims at evaluating the impacts of pyrolysis parameters on the characteristics of eight biochars derived from Miscanthus x giganteus, grown on metal contaminated soils, and selecting the one which may be the most efficient to remediate metals (Cd, Pb, Zn) and/or PAHs contaminated soils. A strong influence of pyrolysis temperature on biochar characteristics was detected. Moreover, biochars showed strong sorption capacity for the three metals and PAHs in aqueous solution, especially for those produced at 600°C. Experiments realized with an artificial soil, and an agricultural soil, both artificially contaminated, demonstrated the efficiency of some biochars to decrease the environmental availability, bioavailability and oral bioaccessibility of the metals and PAHs. Based on the results, one biochar was selected as being the most efficient to manage the contaminated soils. In view of the structural modifications of biochars in soils, these results should be validated in situ on long term basis, while ensuring the harmless effects of the studied biochar and integrating the socio-economic aspects.

L’ancienne fonderie de plomb Metaleurop Nord a rejeté énormément de métaux dans l’environnement qui est très dégradé du fait de cette contamination et de la fragmentation des paysages. L’objectif principal du travail de thèse a été de s’interroger sur quel est/sont le(s) meilleur(s) aménagement(s) pour favoriser une reconnexion et une restauration d’une fonctionnalité des sols les plus contaminés sur le secteur ? Trois expérimentations ont été menées sur le terrain. La première dresse un état de la fonctionnalité de sols de parcelles anciennement boisées à travers la comparaison d’un panel de 55 indicateurs physico-chimiques et biologiques Les deux autres s’intéressent à l’influence d’un aménagement, l’une en étudiant l’influence de la composition pariétale des essences et la pollution métallique des litières, l’autre tournée d’avantage sur le processus de dégradation de la litière. L’étude de la recolonisation des milieux dégradés, à l’aide de la technique du mulching, a été réalisée à travers la mise en place d’une expérimentation sur le terrain qui a été suivie 2 ans. Les principales conclusions de ce travail en terme de préconisations sont de favoriser les plantations mixtes et les essences locales, prendre en compte les types de sol (teneurs en CaCO3, hydromorphie, concentrations en métaux…) et les exigences écologiques des essences envisagées, amender les sols avec des amendements minéraux ou organo-minéraux afin de limiter la mobilité des métaux, varier les densités de plantation afin de favoriser un maximum d’espèces, développer des zones de transition entre les milieux et accélérer le processus de colonisation via la technique du mulching.h / The former lead smelter Metaleurop Nord has rejected a lot of metals to environment which is immensely degraded due to this contamination and fragmentation of landscapes. The main aim of this thesis was to ask what is / are the best layout (s) to promote a reconnection and restoration of a feature of the contaminated agricultural soils of the site "Metaleurop"? Three experiments were conducted in the field. The first gave the state of the functionality of floor formerly woodlots plots and three references (a wood, a hedge and an agricultural system) through comparison of a panel of 55 physico-chemical and biological Indicators. Two others were interested in the influence of management; one in studying the influence of the parietal species composition and metal pollution, another tour more about the litter degradation process was realized with the litterbags technique. The study of the recolonization of degraded environments, using a simple landscaping technique (mulching), was achieved through the establishment of a field experiment which was followed for two consecutive years. Main conclusions of this work in terms of recommendations are: promoting mixed plantations and local species, taking into account soil types (levels of CaCO3, waterlogging, metal concentrations ...) and ecological requirements of the proposed species, amending soils with mineral or organo-mineral amendments to limit the mobility of metals, varying planting densities to promote maximum species, developing transition zones between environments and accelerating the process of colonization through the technical mulching.

De nombreux sols contaminés par les éléments métalliques résultent des activités humaines et industrielles. Pour gérer ces sols, la technique du phytomanagement a séduit les scientifiques et les gestionnaires des sites pollués. Tout en utilisant le génie végétal, cette technique permet de produire des biomasses qu’il convient de valoriser. Sur la base de cette approche, le présent travail décrit cette technique en utilisant des biomasses (raygrass et miscanthus) en association à des amendements phospho-calciques. Ces biomasses, décrites comme étant non-hyper-accumulatrices des éléments métalliques, ont été produites sur des terres de jardins et des terres agricoles. Les expérimentations ont été menées en serre, en mésocosme, et in situ, à proximité de l’ancienne fonderie de plomb Metaleurop Nord.L’utilisation raisonnée des composés phospho-calciques n’a pas affecté significativement les caractéristiques physico-chimiques et biologiques des sols. En revanche, il a pu être montré une amélioration de certains paramètres physiologiques des plantes. Par ailleurs, les composés phospho-calciques ont généralement réduit l’extractabilité et la phytodisponibilité de Cd et Pb tout en favorisant la mobilité et le transfert d’éléments d’intérêt vers les parties aériennes des biomasses. Ceci a permis de transformer ces biomasses en écocatalyseurs. Après avoir été caractérisés, ces derniers ont été utilisés en synthèse organique et leur recyclabilité a été montrée. Trois exemples ont été présentés dans le cadre du présent travail. Dans une perspective d’utilisation d’autres biomasses, les concentrations en éléments métalliques dans des plantes rudérales ont été déterminées. / Many metal-contaminated soils result from human and industrial activities. To manage these soils, the phytomanagement has attracted scientists and managers of contaminated sites. While using plant engineering, this technique produces biomass that should be valued. Based on this approach, the present work describes this technic by using plant biomass (ryegrass and miscanthus) in combination with phosphocalcic amendments. These biomass, described as non-hyper-accumulators, were produced on garden soils and agricultural soils. The experiments were conducted in greenhouse, mesocosm and in situ near the former Metaleurop Nord smelter. The sustainable use of phosphocalcic compounds did not significantly affect the physicochemical and biological characteristics of soils. In contrast, some physiological parameters of plants were improved. In addition, the phosphocalcic compounds decreased the extractability and phytavailability of Cd and Pb in some cases while promoting the mobility and the transfer of other metallic elements from the soil to the aerial parts of the biomass studied. Metal-enriched biomass were transformed into ecocatalysts. After being characterized, these ecocatalysts were used in organic synthesis and their recyclability was demonstrated. Three examples have been detailed in the current thesis report. In view of using other biomass, metal concentrations in ruderal plants were determined.

Determining the total concentration of elements in soils seldom provides sufficient insight into trace metal bioavailability. However, measurement of ‘isotopically exchangeable’ metal can provide a better evaluation of metal reactivity and potential toxicity. Traditionally this requires the use of problematic radio-isotopes (e.g. 109Cd (γ)). Fortunately, increasing access to Inductively Coupled Plasma Mass Spectrometry (ICP-MS) in recent years has led to greater use of enriched stable isotopes of trace metals. The lability of heavy metals has been determined through a variety of approaches, including single and sequential extraction or predicted by geochemical models. In the present work, multi-element stable isotopes methods were developed for simultaneously determination of the labile pool of Fe, Zn, Cd and Pb using isotopic exchange principles. This included experimental and instrumental development for an accurate and precise determination of labile metal pool in soils. This approach was then validated by quantifying Zn, Cd and Pb in contaminated soils (Derbyshire; n = 8 and Weardale catchment; n = 246) and comparing the outcome results with common traditional extraction procedures. The variation of metal lability with soil characteristics was used to predict metal lability from the simple soil measurements using a multiple regression approach. In addition, E-values of Fe, Zn, Cd and Pb was used as input to WHAM(VI) (Windermere Humic-Aqueous Model) to predict metal solubility, emphasising in the role of Fe under reducing conditions in this regard. The results showed that isotopic dilution is a robust mechanistic method for assessing the ‘reactive’ pool of multiple trace metals over a wide range of soil characteristics. The results showed a very wide range of metal reactivities (almost 1%-100%) for Zn, Cd and Pb that were consistent over a range of spike concentrations. Sub-micron forms of non labile metal are perhaps most likely to occur in suspension either strongly bonded to humic/fulvic acids or occluded within CaCO3 particles. It appears that E values have no consistent correspondence to any chemical extraction procedure. Nevertheless, the use of 0.43 M HNO3 to extract labile metal in organic soils at pH < 6 appears justifiable - especially where humus is likely to be the principal adsorption surface. It is also important to acknowledge that extractions are not necessarily intended to estimate the entire reactive fraction. Thus, DTPA has been successfully applied as an empirical prediction of plant uptake but its extraction capacity is particularly limited in calcareous systems where it substantially underestimates the isotopically exchangeable metal pool. Speciation calculations showed that prediction of metal solubility was much better when the isotopically reactive metal pools were used as input to WHAM(VI). The soil samples that fitted best had pH values less than 4.0 and high organic matter contents reflecting the strength of the humic binding component of WHAM(VI) particularly in the case of Zn. The changes in metal solubility and lability under reducing conditions were mainly affected by pH. Moreover, the measurement of Fe2+ in the solution phase was considerably lower than that of the isotopically labile Fe2+ which calls into question the dependence on soluble Fe2+ to predict reductive dissolution of Fe-oxides. In addition, under reducing conditions the variables input of Fe to WHAM(VI) showed greatest effects on predicting metal solubility. It was found that Zn and Cd were affected only by Fe2+ competition for adsorption sites while predicted Pb solubility was more affected by loss of oxides than competition processes. The fractionation results, output from WHAM(VI), showed that a significant proportion of Pb was associated with Mn-oxides. Therefore, the calculation of loss of the adsorption site of Mn-oxides depending on Mn2+ measured in the solution phase did not improve the predicted Pb solubility where the model underestimate the adsorbed labile Mn as inference from Fe results.

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A literature survey has been undertaken of the sources, levels and effects of heavy metal pollution in the urban street environment. Established techniques for the determination of heavy metal levels in urban dusts have been reviewed, and appropriate methods selected for use in the research project. Spatial and temporal variations of Cd, Cu, Pb and Zn in street dust have been investigated at a number sites. Metal loadings showed stronger spatial variation than concentrations with the greatest metal loadings occurring in the gutters and kerbsides. The results have been assessed in terms of surface type and condition, traffic loadings and antecedent weather conditions. The chemical associations of heavy metals in street dust, and their relationships to particle size have been investigated. Lead and Zn were associated mainly with carbonates and Fe-Mn oxides, whereas Cu is largely found in the organic fraction. Cadmium shows the greatest affinity for the exchangeable phase, and is therefore considered the most environmentally mobile metal studied. In addition to the studies mentioned above levels and chemical associations of heavy metals In school playground dust contaminated by paint flakes have been investigated. The levels of Pb were much higher than those previously reported. Exchangeable Pb concentrations represented a significant hazard to children playing in the area. In addition to the studies mentioned above levels and chemical associations of heavy metals In school playground dust contaminated by paint flakes have been investigated. The levels of Pb were much higher than those previously reported. Exchangeable Pb concentrations represented a significant hazard to children playing in the area. The final stage of the research project involved the operation of a sampling network to establish a mass balance for Cd, Cu, Pb and Zn within a residential urban street. Metal levels in atmospheric deposition, street sediments and runoff were monitored over an eight week period. Stormwater runoff was found to remove only a minor fraction of the metal deposited in the catchment during the sampling period.