Phytoextraction du nickel dans les sols ultramafiques d’Albanie La phytoextraction minière est un procédé de récupération des métaux des sols minéralisés naturels ou pollués à l’aide de plantes hyperaccumulatrices. Elle est une alternative à l’agriculture vivrière des zones ultramafiques. L’objectif de la thèse est le développement d’une technologie de phytoextraction extensive du Ni avec Alyssum murale sur les Vertisols ultramafiques. Pour cela, il s’agissait : i) d’identifier les plantes hyperaccumulatrices les plus efficaces dans le prélèvement du Ni et comprendre les relations entre le prélèvement du métal et sa biodisponibilité, ii) de déterminer les types de sols adaptés à la phytoextraction du Ni et iii) de définir et optimiser un itinéraire agronomique adapté pour l’espèce retenue et pour les conditions édaphiques. Dans ce but, des prospections géobotaniques ont été conduites en Albanie et en Grèce. Puis une étude in situ des facteurs qui influencent la biodisponibilité du Ni et le comportement des plantes sur une toposéquence ultramafique a été mise en place. Enfin un essai agronomique de quatre années sur un site ultramafique d’Albanie (Pojske) a permis de tester la fertilisation, le contrôle des adventices par herbicide et la date de récolte pour optimiser le rendement d’extraction du Ni. Les résultats montrent que parmi l’ensemble des espèces présentes naturellement sur les serpentines des Balkans, A. markgrafii et A. murale ont le plus fort taux d’accumulation du Ni. Les Vertisols ultramafiques présentent une disponibilité élevée du Ni favorable à la phytoextraction minière. La biomasse d’A murale est augmentée de 0,2 t ha-1 à 6,0 t ha-1 à partir des traitements agronomiques et le rendement de phytoextraction de Ni par A. murale est de 23 à 69 kg ha-1. Alyssum murale peut être envisagée comme une culture pérenne et la fertilisation permet d’augmenter la compétitivité de la plante sans affecter les concentrations de Ni dans les parties récoltées / Phytomining is a process for recovering metals with hyperaccumulating plants from natural or polluted soils. It is an alternative to conventional farming in ultramafic areas. The aim of the thesis is the development of an extensive phytoextraction technology with Alyssum murale on ultramafic Vertisols. Therefore, work was conducted to i) identify the most effective Ni hyperaccumulators, and understand the relationship between metal uptake and bioavailability, ii) identify soil types suitable for phytoextraction, and iii) define and optimize agronomic practices adapted to the plant species and the edaphic conditions. Hence, geobotanical surveys were conducted in Albania and Greece. Then an in situ study was run on an ultramafic toposequence to assess the factors that influence Ni bioavailability and behavior of plants. Finally a four-year field trial was carried out on an ultramafic site in Albania (Pojske) where fertilization, weed control by herbicide, and harvest date were tested to optimize the efficiency of Ni extraction. The results showed that A. markgrafii and A. murale exhibit the highest rate of Ni accumulation among all species of Balkan serpentines. The ultramafic Vertisols have a high Ni availability phytoextraction and are favourable for phytomining. A. murale biomass increased from 0.2 t ha-1 to 6.0 t ha-1 due to optimization of agronomic treatments, and performance of phytoextraction from 23 to 69 kg ha-1. Alyssum murale can be seen as a perennial crop, and fertilization increases the competitiveness of the plant without affecting the Ni concentrations in the harvested parts

Pharmaceutically Active Compounds include metformin, the most often prescripted drug for a treatment of the diabetes mellitus type 2. Metformin is used in high daily doses (up to 3000 mg per day) and it is eliminated by kidneys in its original non - metabolized form. Metformin is degraded in the wastewater treatment plants to guanylurea. The wastewater treatment plants aren't able to clean the waste water, so metformin and guanylurea enter the environment, especially surface water. This diploma thesis deals with the ability to remove metformin and its environmental metabolite guanylurea via phytoextraction technologies. First experiment was focused on phytoextraction of metformin using 5 plant species - Zea mays L., Pisum sativum L., Avena sativa L., Alternanthera reineckii Mini L. and Staurogyne repens L. Second experiment studied phytoextraction of guanylurea using Zea mays L. and Pisum sativum L. The third experiment deals with the phytoextraction of metformin and guanylurea together using Zea mays L. The media of all plants were contaminated by metformin or guanylurea at different concentration levels. The samples of media were taken in 24 hours intervals during the plant cultivation and the decrease of its concentration were studied by HPLC with UV detection at 233 nm for metformin and 210 nm...

Depuis le début des années 1990, différentes stratégies de phytoremédiation ont été proposées pour réhabiliter les zones polluées par des éléments traces métalliques (ETM). Parmi ces stratégies, la phytoextraction consiste en l’absorption et l’accumulation par les plantes des ETM présents dans les sols. Afin de mettre en place cette stratégie, il a été proposé d’utiliser le peuplier en raison de sa croissance rapide, de son importante biomasse et de ses débouchés énergétiques. Cependant une proportion considérable des métaux absorbés par cet arbre est accumulée dans les feuilles alors que celles-ci chutent à l’automne. Ainsi, l’efficacité de phytoextraction du peuplier peut se trouver limitée si aucun mécanisme de remobilisation des ETM n’est mis en place au cours de la sénescence automnale. Dans ce contexte, une partie des travaux de cette thèse a été réalisée sur la parcelle expérimentale de Pierrelaye polluée suite à l’épandage d’eaux usées de la ville de Paris. Nous avons recherché parmi les 14 génotypes de peuplier présents sur le site, ceux qui sont les plus efficaces pour remobiliser les métaux des feuilles vers les parties pérennes. Des mesures de contenu en métaux, d’expression de gènes et des analyses corrélatives ont ouvert de nouvelles pistes concernant la gestion des métaux foliaires. Parce que la vacuole constitue le principal lieu de stockage des métaux de la cellule, les protéines d’efflux vacuolaire NRAMP (Natural Resistance-Associated Macrophage Protein) précédemment identifiées chez Arabidopsis thaliana, représentent de bons candidats pour stimuler la remobilisation des métaux foliaires. La caractérisation de leurs homologues chez le peuplier a donc été entreprise par expression chez la levure et chez A. thaliana. Afin de contrôler indépendamment le transport des métaux essentiels et non-essentiels chez les NRAMP, une étude visant à identifier les déterminants structuraux impliqués dans leur sélectivité a été réalisée. La caractérisation des mutants NRAMP affectés dans leur sélectivité par expression chez A. thaliana a mis en lumière leur impact sur l’accumulation et la tolérance aux métaux. Dans le but d’étudier l’implication de mécanismes plus généraux de recyclage des nutriments dans la remobilisation des métaux au cours de la sénescence foliaire, le rôle de l’autophagie a été testé chez A. thaliana. L’étude de plantes déficientes pour l’autophagie a montré l’implication de ce mécanisme dans l’efficacité d’utilisation des métaux et probablement dans leur remobilisation au cours de la sénescence. En combinant des études en champ sur le peuplier et de génétique moléculaire chez Arabidopsis, ce travail permet de proposer différentes pistes pour diminuer spécifiquement l’accumulation des ETM dans les feuilles de peuplier. / Since the early 1990s, various strategies have been proposed to rehabilitate trace element (TE) polluted areas by phytoremediation. Among these strategies, phytoextraction consists in TE uptake from soil and accumulation by plants. To implement this strategy, it has been proposed to use poplar due to its fast growth, its large biomass and its use in energy production. However, a substantial proportion of absorbed metals is accumulated in poplar leaves which fall in autumn. Thus, poplar phytoextraction efficiency may be limited if TE are not re-mobilized during autumn senescence. In this context, part of this thesis work has been carried out on the experimental field of Pierrelaye which was polluted by the spreading of sewage water from Paris. Among the 14 poplar genotypes growing on the field, we tried to identify those that efficiently remobilize leaf metals to perennial organs. Metal content, gene expression and correlative analyses have been undertaken, providing new insight in the management of metals in leaves. Because the vacuole is the main metal storage compartment in the cell, NRAMP (Natural Resistance-Associated Macrophage Protein) vacuolar efflux proteins previously identified in Arabidopsis thaliana are good candidates to enhance leaf metal remobilization. Characterization of their homologues in poplar was therefore undertaken by expression in yeast and in A. thaliana. In order to independently control the transport of essential and non-essential metals by NRAMP, a study aiming to identify the structural determinants involved in selectivity was undertaken. Expression of NRAMP mutants affected in their selectivity in A. thaliana highlighted their impact on metal accumulation and tolerance. To study the involvement of more general nutrient recycling mechanisms in metal remobilization during leaf senescence, the involvement of autophagy was tested in A. thaliana. Physiological characterization of autophagy deficient plants indicated that this mechanism plays a role in metal use efficiency and probably in metal remobilization during senescence. By combining a field approach on poplar and molecular genetics in Arabidopsis, this work opens multiple perspectives to specifically reduce the accumulation of TE in poplar leaves.

Les traitements phytosanitaires intensifs en viticulture, conjugués aux flux de ruissellement, se traduisent par l'arrivée de cuivre dans les bassins d'orage (BO). Des phénomènes de bioatténuation impliquant la microflore et les macrophytes s'observent, mais les niveaux d'épuration sont souvent faibles et variables. La phytoextraction du Cu est une technique intéressante in situ mais sa lenteur la pénalise. La bioaugmentation couplée à la phytoremédiation est une solution pour augmenter la vitesse d'extraction. L'étude a consisté à sélectionner un triplet «bactérie-plante-sorbant » afin d'extraire le Cu du sédiment et de réduire sa teneur dans les eaux en sortie de BO. Les trois composantes ont ensuite été assemblées dans des microcosmes remplis d'un mélange sable-sédiment reproduisant les caractéristiques d'un BO de référence. Sur 564 isolats bactériens cultivables, 84 ont montré une capacité à complexer les métaux et l'isolat n°l06 a été retenu pour sa capacité à complexer le Cu. Des trois macrophytes testés, Phragmites australis, espèce retenue dans la suite de l'étude, a accumulé le plus de Cu dans les parties aériennes. Enfin, la pulpe de betterave s'est révélée être le sorbant le plus efficace dans une matrice complexe et en présence d'herbicides. Des expériences en microcosmes, mettant enjeu le triplet sélectionné, ont été réalisées. La localisation de la pulpe de betterave en sortie de microcosmes a réduit de 20% les quantités de Cu exportées par les eaux en atteignant un abattement de 95%. La phytoextraction du Cu a été augmentée par 1,7 grâce à la bioaugmentation dans le cas d'un régime hydraulique semi-continu et d'une inoculation répétée de l'isolat n°106. / Intensive pesticides use in viticulture combined with runoff often result in amounts of Cu getting to storm basins (SB). Biological pesticide mitigation has been observed and related to the role of natural macrophyte together with their associated microflora. Nevertheless, low and variable mitigation levels are most often reported. Cu phytoextraction is a promising in situ technology but requires time. Bioaugmentation-assisted phytoextraction is a new technology that may enhance the phytoextraction rate. The study consisted in selecting the best "microorganism-plant-sorbent" association in order to extract Cu from sediments and mitigate Cu load in SB outlet waters. The association of these three selected components has been studied in SB-scaled microcosms filled with a sand-sediment mixture to a better understanding of the depollution process feasability. Among the 564 isolates extracted from SB sediments, 84 were able to complex metals and isolate 106 was selected for the process implementation on the base of its ability to complex Cu. On the 3 studied macrophytes, Phragmites australis accumulated more Cu in aerial parts. Finally, sugar beet pulp has been selected as the best Cu sorbant in mixture with herbicides and in a complex matrix. Microcosm experiments that associated the best three components were carried out. Results showed that sugar beet pulp located at the outlet of microcosms reduced significantly (20 %) Cu amounts in outlet waters to reach a mitigation rate of 95%. Cu extraction in aerial parts of P. australis has been improved by a factor of 1,7 thanks to an intermittent wate Joad, with drying and rewetting periods along with repeated inoculations.

Dans le contexte de la rareté croissante des ressources naturelles non renouvelables, le génie pédologique permet de construire des Technosols fertiles exclusivement à partir du recyclage de sous-produits industriels délaissés. Cependant, la croissance des plantes peut être limitée par différentes contraintes liées à la présence de contaminants inorganiques dans les matériaux utilisés. L’agromine, qui vise à recycler les métaux stratégiques de l’environnement, représente alors une stratégie écologique et prometteuse pour la gestion durable de ces agrosystèmes. Afin de mieux comprendre les processus contrôlant la pédogenèse et l’évolution des Technosols, ainsi que le potentiel d’agromine sur ces sols, une série d’expériences en conditions contrôlées et sur le terrain ont été réalisées avec (i) Noccaea caerulescens, espèce hyperaccumulatrice de Cd, Ni et Zn (ii) sur des Technosols construits à partir de matériaux délaissés contaminés ou non en métaux (iii) amendés ou non en produits résiduaires organiques (compost ou biochar). A l’échelle du terrain, les résultats attestent que les propriétés des Technosols construits sont fortement influencées par les matériaux parents utilisés. Les sous-produits industriels utilisés dans la construction de sol peuvent avoir un effet initial indésirable pour la production de biomasse végétale due à l’augmentation de la salinité du sol. Une caractérisation fine de la spéciation des métaux a mis en évidence une évolution très rapide des Technosols, en particulier, la dissolution et la lixiviation des phases minérales solubles et la formation de nouvelles phases sorbantes (oxydes de Fe et de Mn) réduisant la disponibilité chimique des métaux. En conditions contrôlées, les amendements en biochar ou en compost tendent à améliorer la disponibilité en éléments nutritifs. Ceci peut être attribué à l’augmentation des activités enzymatiques et de la diversité microbienne, tant structurelle que fonctionnelle, en particulier lors d’addition de compost. Il en résulte une augmentation des teneurs en éléments essentiels dans les parties aériennes de la plante. Concernant les éléments en traces, l’addition au sol de biochar conduit à une diminution de leur disponibilité, alors qu’un effet inverse a été observé lors d’addition de compost. Toutefois les deux amendements augmentent les teneurs en métaux dans les parties aériennes avec un effet supérieur du compost par rapport au biochar. Ainsi, l’espèce hyperaccumulatrice Noccaea caerulescens a montré son aptitude à s’établir sur des Technosols peu fertiles et à concentrer Cd et Zn à des valeurs supérieures au seuil d’hyperaccumulation démontrant la faisabilité de l’agromine de ces métaux. Par ailleurs, les deux amendements organiques semblent pertinents pour améliorer la phytoextraction sur des Technosols construits. / In the context of the increasing scarcity of non-renewable natural resources, the soil engineering has already allowed to build fertile Technosols exclusively from the recycling of abandoned industrial byproducts. However, it has also been shown that plant growth can be limited by various constraints related to the presence of inorganic contaminants in the used materials. Therefore agromining, which aims to recycle strategic metals from the environment, represents a promising strategy for ecological and sustainable management of these agricultural systems. To better understand the processes controlling pedogenesis and evolution of Technosols and the potential of agromining on these soils, a series of experiments in controlled conditions and field were performed with (i) Noccaea caerulescens, a hyperaccumulator species of Cd and Zn, (ii) on Technosols constructed from abandoned materials (iii) amended or not with organic compounds (compost or biochar). At the field scale, the results attest that Technosols properties are strongly influenced by the used parent materials. Industrial by-products used in soil construction can have an adverse effect for the initial plant biomass production due to the increase in soil salinity. A detailed characterization of metal speciation highlighted a very rapid evolution of Technosols in particular the dissolution and leaching of soluble mineral phases and the formation of new sorbent phases (Fe oxides and Mn) reducing the chemical availability metals. Under controlled conditions, biochar or compost amendments tend to improve nutrient availability. This can be attributed to the increase in enzyme activities and microbial diversity, at both structural and functional level, particularly in case of compost addition. This results an increase of essential elements content in the aerial parts of the plant. Regarding trace elements, adding to the soil biochar leads to a decrease of their availability, while an opposite effect was observed during compost addition. However, the two amendments increase the concentration of metals in shoots with a superior effect of compost with respect to biochar. Thus, hyperaccumulator species Noccaea caerulescens has shown its ability to establish on low fertility Technosols and concentrate high levels of Cd and Zn above the threshold of hyperaccumulation demonstrating then the feasibility of agromining of these metals. Moreover, both amendments appeared relevant to improve phytoextraction from abandoned industrial materials.

Les fortes tensions liées à l'approvisionnement en ressources minérales ont motivé de nombreuses recherches sur les substitutions innovantes et le recyclage. La biomasse riche en métaux produite par les techniques de phytoextraction s'est récemment avérée être une ressource pour la Chimie Verte. Cette biomasse permet de produire de nouveaux catalyseurs appelés « écocatalyseurs ». Ceux-ci permettent la production de nouvelles molécules, des meilleurs rendements en synthèse, une régio- et une chimio-sélectivité accrues… Ceci donne une valeur ajoutée potentielle et donc le possible développement d'une filière économique. Cette nouvelle approche pourrait motiver le développement de la phytoextraction, une technique considérée comme prometteuse, mais qui après 20 années de recherches n'a toujours pas trouvé de débouché crédible. Dans ce cadre, les haut lieux de la biodiversité « métallophyte », tels que la Nouvelle-Calédonie, ont leur importance pour évaluer l'approvisionnement en biomasse. En Nouvelle-Calédonie, l'ambitieuse et coûteuse restauration écologique de ces écosystèmes miniers très dégradés est mise en doute. Dans ce cas, le développement de la phytoextraction sur les carrières et verses à stériles pourrait apporter des revenus, tout en assurant une forme de réhabilitation. Cette thèse s'intéresse à la possibilité d'une filière en Nouvelle-Calédonie, de la plante au produit chimique en passant par le catalyseur. / Increasing pressure on mineral resources has drawn research efforts into innovative supply and recycling. Metal-rich biomass produced in phytoextraction proved an interesting starting-material for Green Chemistry. It allows the production of new catalysts, referred to as ‘ecocatalysts'. They provide the following benefits: access to new molecules, increased yields in chemicals production, increased regio- and chemo-selectivity… This results in potentially high added-value and possible development of a new economic outlet. This new approach to using metal-rich biomass could spur the development of phytoextraction, a technique considered promising for long, yet without credible economic applications. In this regard metallophyte biodiversity hotspots, such as New Caledonia are of particular interest to assess biomass supply. Ambitious and costly ecological restoration of the mining environment in New Caledonia is increasingly questioned. The development of phytoextraction on most degraded areas, e.g. quarries and wastes piles, to produce biomass for Ecocatalysis could provide revenues, while ensuring reclamation. This thesis looks into a possible outlet in New Caledonia, from plants to catalysts and final chemical products.

No description available.

<p>Mercury (Hg) pollution is a global environmental problem. Numerous Hg-contaminated sites exist in the world and new techniques for remediation are urgently needed. Phytoremediation, use of plants to remove pollutants from the environment or to render them harmless, is considered as an environment-friendly method to remediate contaminated soil <i>in-situ</i> and has been applied for some other heavy metals. Whether this approach is suitable for remediation of Hg-contaminated soil is, however, an open question. The aim of this thesis was to study the fate of Hg in terrestrial plants (particularly the high biomass producing willow, <i>Salix spp</i>.) and thus to clarify the potential use of plants to remediate Hg-contaminated soils.</p><p>Plants used for phytoremediation of Hg must tolerate Hg. A large variation (up to 30-fold difference) was detected among the six investigated clones of willow in their sensitivity to Hg as reflected in their empirical toxicity threshold (TT_95b), the maximum unit toxicity (UTmax) and EC50 levels. This gives us a possibility to select Hg-tolerant willow clones to successfully grow in Hgcontaminated soils for phytoremediation.</p><p>Release of Hg into air by plants is a concern when using phytoremediation in practice. No evidence was found in this study that Hg was released to the air via shoots of willow, garden pea (<i>Pisum sativum</i> L. cv Faenomen), spring wheat (<i>Triticum aestivum</i> L. cv Dragon), sugar beet (<i>Beta vulgaris </i>L. cv Monohill), oil-seed rape (<i>Brassica napus</i> L. cv Paroll) and white clover (<i>Trifolium repens</i> L.). Thus, we conclude that the Hg burden to the atmosphere via phytoremediation is not increased.</p><p>Phytoremediation processes are based on the ability of plant roots to accumulate Hg and to translocate it to the shoots. Willow roots were shown to be able to efficiently accumulate Hg in hydroponics, however, no variation in the ability to accumulate was found among the eight willow clones using CVAAS to analyze Hg content in plants. The majority of the Hg accumulated remained in the roots and only 0.5-0.6% of the Hg accumulation was translocated to the shoots. Similar results were found for the five common cultivated plant species mentioned above. Moreover, the accumulation of Hg in willow was higher when being cultivated in methyl-Hg solution than in inorganic Hg solution, whereas the translocation of Hg to the shoots did not differ.</p><p>The low bioavailability of Hg in contaminated soil is a restricting factor for the phytoextraction of Hg. A selected tolerant willow clone was used to study whether iodide addition could increase the plant-accumulation of Hg from contaminated soil. Both pot tests and field trials were carried out. Potassium iodide (KI) addition was found to mobilize Hg in contaminated soil and thus increase the bioavailability of Hg in soils. Addition of KI (0.2–1 mM) increased the Hg concentrations up to about 5, 3 and 8 times in the leaves, branches and roots, respectively. However, too high concentrations of KI were toxic to plants. As the majority of the Hg accumulated in the roots, it might be unrealistic to use willow for phytoextraction of Hg in practice, even though iodide could enhance the phytoextraction efficiency.</p><p>In order to study the effect of willow on various soil fractions of Hg-contaminated soil, a 5-step sequential soil extraction method was used. Both the largest Hg-contaminated fractions, i.e. the Hg bound to residual organic matter (53%) and sulphides (43%), and the residual fraction (2.5%), were found to remain stable during cultivations of willow. The exchangeable Hg (0.1%) and the Hg bound to humic and fulvic acids (1.1%) decreased in the rhizospheric soil, whereas the plant accumulation of Hg increased with the cultivation time. The sum of the decrease of the two Hg fractions in soils was approximately equal to the amount of the Hg accumulated in plants. Consequently, plants may be suitable for phytostabilization of aged Hg-contaminated soil, in which root systems trap the bioavailable Hg and reduce the leakage of Hg from contaminated soils.</p>

Mercury (Hg) pollution is a global environmental problem. Numerous Hg-contaminated sites exist in the world and new techniques for remediation are urgently needed. Phytoremediation, use of plants to remove pollutants from the environment or to render them harmless, is considered as an environment-friendly method to remediate contaminated soil in-situ and has been applied for some other heavy metals. Whether this approach is suitable for remediation of Hg-contaminated soil is, however, an open question. The aim of this thesis was to study the fate of Hg in terrestrial plants (particularly the high biomass producing willow, Salix spp.) and thus to clarify the potential use of plants to remediate Hg-contaminated soils. Plants used for phytoremediation of Hg must tolerate Hg. A large variation (up to 30-fold difference) was detected among the six investigated clones of willow in their sensitivity to Hg as reflected in their empirical toxicity threshold (TT95b), the maximum unit toxicity (UTmax) and EC50 levels. This gives us a possibility to select Hg-tolerant willow clones to successfully grow in Hgcontaminated soils for phytoremediation. Release of Hg into air by plants is a concern when using phytoremediation in practice. No evidence was found in this study that Hg was released to the air via shoots of willow, garden pea (Pisum sativum L. cv Faenomen), spring wheat (Triticum aestivum L. cv Dragon), sugar beet (Beta vulgaris L. cv Monohill), oil-seed rape (Brassica napus L. cv Paroll) and white clover (Trifolium repens L.). Thus, we conclude that the Hg burden to the atmosphere via phytoremediation is not increased. Phytoremediation processes are based on the ability of plant roots to accumulate Hg and to translocate it to the shoots. Willow roots were shown to be able to efficiently accumulate Hg in hydroponics, however, no variation in the ability to accumulate was found among the eight willow clones using CVAAS to analyze Hg content in plants. The majority of the Hg accumulated remained in the roots and only 0.5-0.6% of the Hg accumulation was translocated to the shoots. Similar results were found for the five common cultivated plant species mentioned above. Moreover, the accumulation of Hg in willow was higher when being cultivated in methyl-Hg solution than in inorganic Hg solution, whereas the translocation of Hg to the shoots did not differ. The low bioavailability of Hg in contaminated soil is a restricting factor for the phytoextraction of Hg. A selected tolerant willow clone was used to study whether iodide addition could increase the plant-accumulation of Hg from contaminated soil. Both pot tests and field trials were carried out. Potassium iodide (KI) addition was found to mobilize Hg in contaminated soil and thus increase the bioavailability of Hg in soils. Addition of KI (0.2–1 mM) increased the Hg concentrations up to about 5, 3 and 8 times in the leaves, branches and roots, respectively. However, too high concentrations of KI were toxic to plants. As the majority of the Hg accumulated in the roots, it might be unrealistic to use willow for phytoextraction of Hg in practice, even though iodide could enhance the phytoextraction efficiency. In order to study the effect of willow on various soil fractions of Hg-contaminated soil, a 5-step sequential soil extraction method was used. Both the largest Hg-contaminated fractions, i.e. the Hg bound to residual organic matter (53%) and sulphides (43%), and the residual fraction (2.5%), were found to remain stable during cultivations of willow. The exchangeable Hg (0.1%) and the Hg bound to humic and fulvic acids (1.1%) decreased in the rhizospheric soil, whereas the plant accumulation of Hg increased with the cultivation time. The sum of the decrease of the two Hg fractions in soils was approximately equal to the amount of the Hg accumulated in plants. Consequently, plants may be suitable for phytostabilization of aged Hg-contaminated soil, in which root systems trap the bioavailable Hg and reduce the leakage of Hg from contaminated soils.

This research study addresses a problem of water pollution caused by heavy and toxic metals Cd, Cr, Cu and Pb. The thesis proposes the use of the technique of phytoremediation using Phragmites australis (PA) plants that have the capacity to absorb and to accumulate such metals in their roots and leaves. The metal uptake and their location of accumulation in the PA plants were determined using flame atomic absorption spectroscopy (FAAS) and transmission electron microscopy (TEM) respectively. Leachates from contaminated plant biomass were mixed with silver nitrate to assess the manufacture of metal nanoparticles as an added value step in the process from remediation to biomass disposal. Silver nanoparticles were readily manufactured by the leachates without, with the exception of copper, any incorporation of the pollutant metal. The presence of copper in the manufactured silver nanoparticles may be of some commercial use. The results obtained show that PA plants will accumulate toxic metals when in hydroponic culture and that the majority of the accumulated metals are sequestered in the roots and do not enter the aerial parts of the plants in significant amounts. Silver nanoparticles were manufactured from the biomass using a low energy route with no additional chemicals, apart from silver nitrate thus reducing the environmental load that would otherwise be present if a chemical means of nanoparticle production was used.