Modélisation de la dispersion atmosphérique des métaux lourds émis par l'industrie énergétique polonaise.De nombreuses études ont mis en évidence les impacts néfastes de la contamination en métaux lourds de l'atmosphère. Une attention particulière est porté au mercure, au plomb et au cadmium qui font l'objet du protocole d'Aarhus sur les métaux lourds (1998). Les parties signataires (incluant la Pologne) s'obligent à réduire les émissions et à obsrver et suivre les niveaux de contamination dans l'environnement.La Pologne est un des plus gros émetteurs de mercure, de plomb et de cadmium en Europe du fait de l'exploitation de centrale à charbon pour la production d'énergie. Des efforts de recherche sont à réaliser pour étudier la contamination par les métaux lourds. Les objectifs de ce travail sont :• de développer et utiliser un modèle pour représenter la dispersion atmosphérique du mercure dans la plate-forme de modélisation numérique Polyphemus.• d'étudier la dispersion en Europe et en Pologne des émissions du secteur de l'industrie énergétique.Pour satisfaire ces objectifs un nouveau schéma chimique pour le mercure a été implémenté dans la plate-forme de modélisation numérique Polyphemus. Une revue de la littérature scientifique a montré que la chimie du mercure restait mal connue. Cela implique des différences dans les modèles établis jusqu'à présent. Ceux-ci diffèrent également de par leur façon de représenter les processus de retrait de l'atmosphère. Le mercure gazeux élémentaire (GEM) présente des concentrations relativement uniformes dans l'espace. Les concentrations des formes oxydées et les dépôts au contraire présentent de forts gradients dans l'espace.Ce travail a mis en évidence la sensibilité des résultats à plusieurs composantes du modèle. Dans le schéma chimique, les chemins d'oxydation du GEM par le radical hydroxyle, l'ozone et les composés bromés dominent en phase gazeuse. En phase aqueuse les réactions de réduction dominent. Toutes ces réactions ont un impact critique sur les concentrations et les dépôts des formes oxydées du mercure mais faible sur le GEM. Dans ce modèle, le dépôt sec du GEM est un des principaux processus de retrait du mercure atmosphérique. Ce relativement fort flux de dépôt de GEM diffère significativement des précédents modèles qui souvent néglige ce processus. Il a également était mis en évidence que les flux de dépôt humide sont sensibles aux paramètres du modèle de lessivage.Les résultats de simulation montrent que l'industrie énergétique est responsable de 80% des dépôts humides de mercure près des grosses sources ponctuelles. La contribution des émissions nationales sur l'ensemble du pays se limite toutefois à un peu plus de 21% pendant l'hiver, lorsque de grandes quantités de charbon sont brûlées. L'impact des émissions de cadmium et de plomb est comparativement plus faible. Les simulations montrent un impact maximal de 30% et 10% pour le cadmium et le plomb respectivement à proximité des sources.De manière générale de plus nombreuses observations de concentrations et de dépôt de métaux lourds seraient utiles pour une meilleure évaluation des modèles / Modelling of atmospheric transport of heavy metals emitted from Polish power sectorMany studies have been conducted to investigate the atmospheric heavy metals contamination and its deposition to ecosystems. The increasing attention to mercury pollution has been mainly driven by the growing evidence of its negative impacts on wildlife, ecosystems and particularly human health. Lead and cadium are also toxics which are being emitted into the atmosphere by anthropogenic as well as natural sources. The harmful influence of these three heavy metals was underlined in the Aarhus Protocol on Heavy Metals of 1998. The Parties of this protocol (including Poland) are obligated to reduce emissions, observe the transport and the amounts of lead, mercury and cadmium in the environment.Poland is one of the biggest emitter of mercury, lead and cadmium in Europe mainly due to emission from coal combustion processes. Therefore in Poland, research efforts to study the heavy metals emission, atmospheric transport, concentration and deposition are extremely important. The objectives of this work were twofold:• The practical objective was to develop and run a model to represent the atmospheric dispersion of mercury and to implement it in the air quality modelling platform Polyphemus.• The scientific objective was to perform heavy metals dispersion studies over Europe and detailed studies of the impact of the polish power sector on the air quality regarding mercury, cadmium and lead.To meet the declared aim, a new mercury chemical model was implemented into the Polyphemus air quality system. The scientific literature was reviewed regarding mercury chemistry and mercury chemical models. It can be concluded that the chemistry of mercury is still not well known. The models also differ in the way of calculating the dry and wet deposition of mercury. The elemental gaseous mercury ambient concentrations are evenly distributed, on the contrary, high variations in the spatial gradients of reactive gaseous and particulate forms of mercury air concentrations and deposition fluxes were noted.This study shows that many components of the developed model have crucial impacts on the results. In the model of mercury chemistry, the most effective pathway in the gaseous phase are the oxidation of gaseous elemental mercury by hydroxyl radical, ozone and most of all bromine oxide radicals, while in the aqueous phase the reduction reactions of elemental mercury dominate. These reactions have a crucial influence on the mass balance of reactive mercury, but a rather low influence on gaseous elemental mercury (GEM). In this model, dry deposition of gaseous elemental mercury is the prevailing process for removing mercury from the atmosphere. Dry deposition of GEM over land is equally distributed, due to almost uniform ambient concentrations. The relatively high dry deposition flux of gaseous elemental mercury has a huge influence on the presented results and differs significantly from other models where the dry deposition of GEM is often not taken into account. It was also shown that a change in the calculation of the scavenging coefficients or representative raindrop diameter for in-cloud scavenging has a significant impact on the amount of wet deposited mercury.The detailed results show that the Polish power sector can be responsible for up to 80% of wet deposited mercury near large emission sources. The contribution from national sources over whole Poland reaches 21% during the winter heating season when large quantities of coal are burned in the domestic sector and additionally the power sector activity is at its highest. The impact of emissions of cadmium and lead from the power sector is lower compared to the obtained results for mercury. The modelling results showed maximal impacts of 30% and 10% for cadmium and lead near large power sector sources on the ambient concentrations and deposition. Wider measurements of heavy metals are very much needed

Ce travail de thèse a porté sur l’étude des méthodes de traitement des sédiments de dragage en vue de leur remédiation et leur valorisation : la méthode électrocinétique et la méthode solidification/stabilisation. Deux dispositifs expérimentaux (à deux échelles différentes) ont été développés et une série d’essais électrocinétiques ont été effectués sous différentes conditions (valeurs du potentiel électrique, système ouvert/fermé, solutions d’électrolyte : EDTA, EDDS, NTA et Acide citrique). Chaque chélatant fournit une efficacité d’extraction sur un métal donné. Les résultats obtenus montrent que le contrôle de pH à la cathode par l’acide citrique et l’ajout d’un tensio-actif (Tween 20) peuvent augmenter l’effet de remédiation des métaux. Par ailleurs, lorsque le système est fermé, l’efficacité d’électroremédiation est plus élevée. Les abattements obtenus pour les métaux dans la matrice des sédiments sous des conditions optimales peuvent atteindre 60 %. Pour ce qui est de la solidification/stabilisation, plusieurs formulations (de chaux, de ciment et de fumée de silice) associées au sédiment ont été testées dans le but de reconstituer un matériau résistant et durable dans l’objectif de son utilisation dans les remblais routiers. Les éprouvettes de sédiment traitées ont été soumises à des conditions sévères de température et d’humidité. Des essais de lixiviation ont été effectués sur le matériau obtenu afin de déterminer la capacité des formulations à stabiliser les éléments polluants contenus dans le sédiment. Les résultats obtenus avec 12 différentes formulations ont montré que la résistance requise est obtenue avec des proportions raisonnables d’ajouts, tandis que l’exigence de durabilité nécessite une plus grande proportion de chaux. / This thesis research is devoted to investigate the treatment methods of dredged sediments in order their restoration and valorisation: electroremediation and solidification/stabilization. Two experimental set-up (at two different scales) have been designed and a series of tests were performed under different conditions (electric potential values, opened/closed system, electrolyte solutions: EDTA, EDDS, NTA and Citric Acid). Each chelating agent provides an extraction efficiency for a given metal. The obtained results show that the pH control at the cathode by citric acid and its combinations with a surfactant (Tween 20) can increase the metal removal effect. Moreover, under closed system condition, metal removal efficiency became stronger. The obtained metal removals values within the matrix of sediment under optimal conditions can reach 60%. As regard to the solidification/stabilization, serval formulations (of lime, cement and silica fume) associated to the sediment were tested in order to create a resistant and sustainable material forwarding to be used as a road embankments. The specimens of treated sediment were submitted to severe conditions of temperature and wettability. Leaching tests were carried out on the obtained material in order to assess a capability of used formulations to stabilize pollutant elements contained in the sediment. The obtained results from 12 different formulations showed that the required resistance is obtained with the reasonable proportions of binders, while the sustainability requirement need higher lime content in the formulation.

Ce travail de recherche porte sur l'optimisation des procédés de lavage de sol permettant le traitement des sites contaminés par des métaux lourds. Cette étude se concentre sur le cycle complet de ce type de traitement, incluant la possibilité de réutilisation et un traitement adapté de la solution de lavage de sol utilisée. La conception et l'exploitation d'un procédé de lavage de sol sont étudiées dans le but d'optimiser leur coût et leur efficacité. Dans ce but, les paramètres et la configuration du réacteur utilisé pour ce procédé sont étudiés en détail à travers des tests à l'échelle du laboratoire, et les cinétiques sont simulées par une modélisation mathématique. Les échantillons de sol utilisés au cours de cette étude proviennent de terres agricoles présentant une forte contamination en cuivre. Parmi plusieurs agents chélateurs de la famille des aminopolycarboxylates, il a été choisi d'utiliser l'acide éthylènediamine-N, N'-disuccinique (EDDS) pour sa biodégradabilité - largement rapportée dans la littérature – et son efficacité importante d'extraction des métaux lourds, y compris du cuivre. Le travail bibliographique a permis d'identifier les deux paramètres cruciaux pour l'optimisation du procédé de lavage de sol : le rapport molaire EDDS : Cu et le rapport liquide-solide (L/S). Des tests réalisés dans un réacteur à agitation continue (RAC) en fonctionnement discontinu ont permis d'étudier l'influence de ces deux paramètres sur le rendement et la cinétique d'extraction du cuivre. L’augmentation du rapport molaire EDDS : Cu a permis une meilleure amélioration de l'efficacité du procédé, comparée à l'augmentation du rapport L/S. Par ailleurs, les tests réalisés en discontinu ont clairement mis en évidence une première étape cinétique rapide au début du traitement, suivie d'une seconde étape d'extraction plus lente jusqu'à la fin du traitement. Il a donc été formulé un modèle empirique basé sur deux termes cinétiques. Les paramètres du modèle ont été calibrés puis validés grâce à deux séries de données expérimentales différentes. Ce modèle permet d'abord d'évaluer la validité de l'hypothèse d'un procédé reposant sur deux étapes cinétiques différentes. Cela représente aussi un nouvel outil pour prévoir l'efficacité du procédé en fonction de l'évolution du ratio molaire EDDS : Cu et du temps de traitement. Les coûts d'exploitation du procédé ont été minimisés en étudiant différentes configurations de traitement. En particulier, deux configurations en réacteur piston ont été analysées et comparées à celle en RAC. Les réacteurs pistons ont été simulés en utilisant plusieurs réacteurs en série et en variant les temps de rétention et le fractionnement de l'injection de la solution de lavage de sol. Comparés à la configuration en RAC, les résultats obtenus en réacteur piston ont montré une amélioration du rendement et de la cinétique d'extraction du cuivre, ainsi qu'une réduction de la quantité de solution de lavage utilisée. Pour finir, un procédé électrochimique a été mis en place pour le traitement et la récupération de la solution d'EDDS utilisée. Des tests en réacteur discontinu ont permis d'optimiser les paramètres de ce procédé (densité de courant, pH et conductivité de la solution de lavage de sol). La solution récupérée a ensuite été utilisée pour d'autres étapes de lavage de sol. Les résultats obtenus ont prouvé l'efficacité du traitement électrochimique pour la récupération de la solution d'EDDS, et permettent d'envisager l'application de cette technique pour réduire le coût des procédés de lavage de sol utilisant l'EDDS / The object of the present research work is the optimization of soil-washing processes applied to heavy metal contaminated soils. The work focuses on the whole cycle of these treatments, including the possible recovery and the proper disposal of the used washing solution. Both the design and the exploitation of a soil washing treatment are investigated, in order to maximize their efficacy, in terms of cost and process efficiency. At this aim process parameters and reactor configurations are studied in details through lab-scale tests, and the observed kinetics are simulated through mathematical modeling. Soil samples used for the experimental activity were collected from an agricultural field located in Southern Italy, mainly contaminated by copper. Among several Aminopolycarboxylate (APC) chelating agents, Ethylenediamine-N,N'-disuccinic acid (EDDS) was selected, for its recognized biodegradability, widely reported in literature works, and its efficiency as extracting agent towards several heavy metals, including Cu. Literature review allowed determining the two most important process parameters to be investigated for washing optimization. The two parameters were identified as EDDS : Cu molar ratio and liquid to soil ratio (L/S). In order to investigate the effect of these parameters on process kinetics and Cu extraction yield, batch washing tests in continuous-stirred tank reactor configuration (CSTR) were carried out. EDDS : Cu molar ratio increase was found to be able to enhance process efficiency more than L/S increase. Batch tests clearly displayed a first fast kinetic step at the beginning of the treatment, followed by a second slower kinetic extraction step, which lasted until the end of the treatment. According to this observation, an empirical mathematical model based on two-kinetic terms was formulated. Model parameters were firstly calibrated and then validated using two different sets of experimental data. The derived mathematical model was useful to assess the validity of the two-kinetic steps process hypothesis, and to provide a tool for process efficiency prediction depending on EDDS : Cu molar ratio and treatment time length. Exploitation costs of the process were minimized studying different treatment configurations. In details two Plug-Flow configurations were analyzed and compared to the CSTR one. The two Plug-Flow configurations were simulated using several reactors in series, varying the detention time of the reactors, and fractionating the injection of the washing solution. Achieved results displayed improvements in terms of Cu extraction yield and process kinetic for the tested Plug-Flow conditions compared to the CSTR one, and showed that the use of a Plug-Flow reactor allows to reduce the amount of required washing solution. Finally, an electrochemical process was tested for the treatment and the recovery of the spent EDDS solution. Batch tests were carried out to optimize electrochemical process parameters (e.g. current density, washing solution pH and conductivity). The recovered solution was also used for a multi-washing test. Results proved the effectiveness of the electrochemical treatment for EDDS solution recovery and its potential application as technique for EDDS-enhanced soil washing costs reduction

The present study was conducted to assess selected heavy metal levels (Cu, Fe, Zn, Ni and Pb) in soil and plants that are irrigated by mixed industrial and domestic wastewater in the Buffalo City region. Three types of samples were studied: soil, water and vegetables (spinach and beetroot). Soil analysis showed that most of the heavy metals were found to be acceptable within the SEPA limits. Most of the heavy metal concentrations found in the wastewater indicate that the water is not suitable for irrigation or for livestock use, according to guidelines from the Department of Water Affairs and Forestry of South Africa. The level of copper in the wastewater effluent exceeded the level specified by SEPA limits. In the wastewater the lead concentration averaged 3.24 and 1.98 ppm in Tshatshu (TS) and Mlakalaka (ML) respectively, which shows that both sites are not suitable for both irrigation and livestock usage. The heavy metal levels (Ni, Pb, and Cu) in both spinach and beetroot samples exceed the criteria specified by the WHO and SEPA standards. The study recommends terminating the usage of effluent for irrigation and further investigation or monitoring in these water sources.

Nous avons fait l'analyse des flux cytométrie nous a permis d'évaluer les changements dans le nombre de cellules de Sertoli et germinales par le cadmium. Seulement cellules germinales ont diminué dans le temps et de manière dose-dépendante. CS fragmenté, asynapsis et "mitée" CS ont été observés. Cd induit modifications ex-vivo en cours de la méiose. BPA changé chronologie de la méiose et active le point de contrôle de pachytène. Asynapsis et la fragmentation ont été induites. Noyaux leptotène anormaux, et zygotène asynapsed, observées. CS pulvérisé indiqué les anomalies de recombinaison et / ou d'appariement génétique.BPA modifie principales fonctions biologiques et les voies canoniques. Le nombre de gènes affectés par BPA a augmenté au cours du temps d'exposition. Changement Fold augmenté. Quatre fonctions altérées étaient le cancer, la mort cellulaire, le développement cellulaire et la cellule de cellulaire signalisation. Nous insistons sur le fait que les gènes liés à l'ADN interagi ORD réparation perturbés.la mesure des métaux dans le plasma séminal et de l'ADN du sperme des hommes normaux et anormaux. Nous avons utilisé ICP / MS pour mesurer la concentration de métal dans l'ADN de le sperme et plasma séminal. Tous les métaux analysés ont été détectés dans le plasma séminal. De l'ADN de sperme, As, Hg, Sb et Se, ont été non détecté par cette méthode. Aucune correlation des concentrations de métaux entre le plasma séminal et d'ADN de sperme ont été observées. Les concentrations de métaux, dans le sperme normaux et anormaux, visualiser une augmentation significative de Sb dans le plasma séminal et de Al dans l'ADN des spermatozoïdes dans le sperme de groupe anormal. / We did Flow cytometric analysis enabled us to evaluate changes in the number of Sertoli cells and germ cells by cadmium. Only germ cells were decreased in a time and dose dependent manner. Fragmented SC, asynapsis and "motheaten" SC were observed. Cd induced ex-vivo modifications in meiotic process. BPA changed meiotic chronology and activates the pachytene checkpoint. Asynapsis and fragmentation were induced. Abnormal leptotene nuclei, and asynapsed zygotene, observed. Pulverized SC indicated the abnormalities of genetic recombination and/or pairing. Transcriptomic analysis showed that BPA alters main biological functions and canonical pathways. The number of genes affected by BPA increased over the exposure time. Fold change increased. Four impaired functions were cancer, cell death, cellular development and cell to cell signaling. We emphasize that interacted genes linked to DNA DSB repair disturbed.The other part of this thesis is including the measurement of metals in seminal plasma and in sperm DNA of normal and abnormal men. We used ICP/MS to measure the metal concentration in the seminal plasma and sperm DNA. All metals analyzed were detected in seminal plasma. In sperm DNA, As, Hg, Sb and Se, were undetected with this method. No correlation between the seminal plasma and sperm DNA metal concentrations were observed. The metal concentrations, in normal and abnormal semen, visualized a significant increase of Sb in the seminal plasma and of Al in the sperm DNA in the abnormal semen group.

CONTEXTE GENERAL: En raison des activités anthropiques, les sols sont souvent contaminés par des métaux lourds et des hydrocarbures pétroliers. Le nombre important de sites multi-contaminés dans l'environnement met en lumière la nécessité de trouver des solutions adéquates à ces scénarios complexes d'assainissement, qui, de plus, sont rarement étudiés. Parmi les techniques d'assainissement biologique, la phytoremédiation est une technique qui se base sur les propriétés naturelles des plantes pour assainir les sols. L'utilisation conjointe des plantes et des microorganismes pour dépolluer les sols multi-contaminés est une stratégie de traitement en plein essor. Cependant, l'obstacle majeur qui entrave la réussite de tels traitements est la faible biodisponibilité des polluants dans le sol. Par conséquent, la phytoremédiation peut être assistée par des traitements chimiques et/ou biologiques afin de surmonter cette limitation et d'améliorer l'efficacité de l'assainissement. Dans cette étude, l'approche chimique implique l'ajout d'amendements biodégradables. Enfin, la stratégie biologique retenue dans ce travail est la bioaugmentation qui consiste à ajouter dans le sol des bactéries capables d'améliorer l'assainissement des polluants et/ou favoriser la croissance des plantes. PRINCIPAUX OBJECTIFS: a) Étudier le potentiel de la luzerne pour la phytoremédiation des sols multi-contaminés, b) Étudier les effets de l'acide organique de faible poids moléculaire acide citrique et le tensioactif Tween® 80 sur le processus de phytoremédiation et c) Étudier l'effet de la bioaugmentation avec la bactérie Pseudomonas aeruginosa sur le processus de phytoremédiation. METHODES: Détermination des taux de germination et de mortalité, évaluation des paramètres physiologiques des plantes. Quantification de la biomasse végétale, des métaux lourds dans les plantes, hydrocarbures pétroliers totaux (HCT) dans le sol, et indicateurs microbiologiques du sol. Calcul des paramètres de phytoremediation.RESULTATS REMARQUABLES: La luzerne a présenté une faible tolérance aux HCT du sol à 8400 mg kg-1 de matière sèche (MS). Celle-ci qui a été améliorée lorsque les HCT étaient présents à plus faible concentration (3600 mg kg-1 MS). La luzerne a été en mesure de prendre les métaux dans une proportion limitée (<100 mg kg-1 MS), tandis qu'elle a eu un effet positif sur le nombre de microorganismes du sol capables de dégrader les alcanes et sur l'activité de la lipase dans la rhizosphère. En outre, l'application combinée de l'acide citrique et du Tween® 80 a donné lieu à une amélioration plus importante de nombre et de l'activité microbienne dans la rhizosphère. La bioaugmentation avec P. aeruginosa a eu un effet sur l'amélioration de la biomasse de luzerne (augmentation de la biomasse végétale sèche totale de 71%). En outre, les taux les plus élevés d'élimination des HCT (68%, après 90 jours d'expérience) ont été obtenues dans les sols plantés avec la luzerne et bioaugmentées par P. aeruginosa. CONCLUSION GENERALE: La luzerne pourrait tolérer le sol co-contaminé par des métaux lourds et des hydrocarbures pétroliers, ce qui est une caractéristique essentielle en phytoremédiation. La luzerne ne peut cependant pas être considérée comme une espèce capable d'extraire activement les métaux lourds, même en présence d'amendements chimiques ou par bioaugmentation. Néanmoins, l'augmentation du nombre et de l'activité microbienne dans la rhizosphère a confirmé le potentiel de cette plante à être utilisée avec succès dans le traitement des hydrocarbures pétroliers. Ces effets ont été par ailleurs renforcés par l'application conjointe d'acide citrique et de Tween® 80. Enfin, la combinaison de la phytoremédiation et de la bioaugmentation semble une approche prometteuse pour réaliser l'assainissement des hydrocarbures pétroliers, lorsqu'ils sont présents dans des sols multi-contaminés / GENERAL BACKGROUND : As a result of anthropogenic activities, soil resources remain contaminated with heavy metals and petroleum hydrocarbons. The high frequency of occurrence of multi-contaminated soils in the environment brings to light the necessity to find remediation solutions adequate in such complex scenarios, which besides have seldom been studied. Phytoremediation is a biologically based remediation technology, which takes advantage of the intrinsic physiological abilities of plants to remediate contaminated media. Plants and their associated microorganisms perform phytoremediation processes (e.g. phytoextraction and rhizodegradation), which can bring about the clean-up of multi-contaminated soils. However, a major constraint which hinders the success of phytotechnologies is low bioavailability of pollutants in soil. As a result, chemically- and biologically-assisted phytoremediation are possible strategies used to overcome this limitation and improve the remediation efficiency. The chemical approach presented in this study involves the addition of biodegradable soil amendments to increase the ability of contaminants to be transferred from a soil compartment to plants and microorganisms. The biological strategy explored herein consists of inoculating contaminated soils with bacteria (bioaugmentation) able to improve remediation of pollutants and/or promote plant features.MAIN OBJECTIVES: a) To investigate the phytoremediation potential of alfalfa (Medicago sativa) in multi-contaminated soils b) To study the effects of the low molecular weight organic acid citric acid and the surfactant Tween® 80 on the phytoremediation process c) To assist phytoremediation with a bioaugmentation approach using Pseudomonas aeruginosa bacteria. METHODOLOGIES: Determination of germination and mortality rates, assessment of plant physiological parameters. Quantification of plant biomass, heavy metals in plants, total petroleum hydrocarbons (TPH) in soil, soil microbiological indicators. Calculation of phytoremediation parameters. REMARKABLE RESULTS : Alfalfa presented low tolerance to TPH contaminated soil at 8400 mg kg-1 soil, which was improved when TPH were present at lower concentration (3600 mg kg-1 soil). Alfalfa was able to take up metals to a limited extent (<100 mg kg-1 dry matter), while had a positive effect in promoting microbial number of alkane degraders and lipase activity in the rhizosphere. Moreover, the combined application of citric acid and Tween® 80 resulted in a greater improvement of these parameters. Bioaugmentation with P. aeruginosa had a promoting effect on alfalfa biomass (71% increase of plant total dry biomass). In addition, the highest TPH removal rates (68%, after 90 days of experiment) were obtained in soils vegetated with alfalfa and bioaugmented with P. aeruginosa.OVERALL CONCLUSION: Alfalfa could tolerate a heavy metal and petroleum hydrocarbon co-contaminated soil (subject to TPH levels), which is an essential characteristic for any plant species to be used in phytoremediation. Alfalfa could not be considered as an actively heavy metal removal species as it was not able to phytoextract significant amounts of heavy metals (still in the presence of soil amendments or bioaugmentation). Nevertheless, the enhancement of microbial number and activity in the rhizosphere encouraged the potential of this plant species to be successfully used in the remediation of petroleum hydrocarbons. These effects were additionally enhanced by the joint application of soil amendments. Finally, the combination of phytoremediation and bioaugmentation seems a promising approach to achieve the remediation of petroleum hydrocarbons, when present in multi-contaminated soils

M.Sc. / Sperm, eggs, free embryos and larvae of the sharptooth catfish, Clarias gariepinus, were used in a series of experiments conducted with zinc and copper salts in a flow-through exposure system. Metal concentrations ranged between 0 to 9mg/1 water. The aim of the study was to determine which of these early life stages was the most sensitive towards these metals and to determine whether the early life stages of the sharptooth catfish could be used for rapid bioassesment studies. Parameters investigated were sperm quality, egg hatchibility, free embryo and larval survival and growth. Within all the parameters tested sperm quality proved to be the least sensitive, with no significant changes noted at the metal concentrations used. There are notable reductions on hatching success embryonic and larval survival and growth as metal concentrations increased. Results revealed that the most sensitive was the free embryo stage directly after, and up to 48 hours after hatching. 48 hour old free embryo displayed 48th L.C.50 values as low as 1.98mg/l for zinc and 0. 0.13mg/l for copper, which indicated that this stage was very sensitive and susceptible to environmental stressors. Since C. gariepinus is an indigeniuos species that is widespread throughout the African continent and considering the sensitivity of the early life stages it is a succesfull candidade for use in rapid bioassessment tests throughout the continent.

M.Sc. / The addition of lignocellulosic fibres to thermoplastic polymers is known to increase the toughness of the polymers but it compromises the tensile strength. On the other hand, inorganic fillers like TiO2 are known to improve the tensile strength of polymers. These plant fibres have been used as adsorbents of metal pollutants in water. Best results were obtained when such materials were ground to fine powder but due to low density, the fibres float and form aggregates in water. Being highly biodegradable in nature makes plant fibres unsuitable for water treatment over lengthy periods of time. They cannot be used as standalone materials. Mixing these adsorbents with polymers, which cannot only act as support for the adsorbents but also disperse the fibres within it thus preventing leaching, is a cause for concern. This study was aimed at fabricating plant fibre-polymer composites that will have improved mechanical and thermal properties. These composites were to be tested for their ability to be used as metal ion adsorbents. The composites were fabricated using a melt-mix compounding method. Two thermoplastic polymers, EVA and PCL were each mixed with either lignin or SCB and TiO2 in different ratios. A rheomex mixer coupled with a single screw extruder which was attached to a sheet die was used to synthesise the composites. TGA and DSC were used for thermal propagation while the mechanical properties were investigated using an instron. Metal ion adsorption measurements were analysed using an atomic absorption spectrometer (AAS). These adsorbents were used to remove Cr(VI), Cr(III) and Pb(II), varying different environmental parameters like pH, concentration, time and adsorbent at constant temperature. The reinforcing effect of both lignin and SCB resulted to poor thermal and mechanical properties. This was shown by a decrease in onset degradation temperature and the tensile and toughness of the composites compared to the neat polymers. The incorporation of TiO2 on SCB-EVA composites, however, improved the mechanical strength and resulted in a thermally stable composite compared to counterpart composites without TiO2. This observation was surpassed at high filler loading as the addition of TiO2 resulted in a decrease of the properties. For the tensile strength, neat EVA recorded 11.35 MPa while 2% TiO2-EVA registered 12.49 MPa for example. For the same composite, the onset degradation temperature for EVA was 353 oC but shifted to 368 oC after the addition of TiO2. At higher filler loading, no effect was observed when adding TiO2.

M.Sc. / Pollutants present in minute concentrations in aquatic environments and which possess long residence times may be accumulated by aquatic organism such as fish, resulting in adverse affects. Bioaccumulation and biomarker responses are often used to qualify and quantify pollutant exposure and effect, and for this reason form a major part of many environmental assessments. To interpret bioaccumulation and biomarker responses the physico-chemical parameters of the environment should be known. This study aimed to spatially and temporally assess the environmental partitioning of heavy metals in three South African freshwater systems, namely the Pongolapoort Dam, Olifants and Luvuvhu Rivers, and to relate these concentrations to bioaccumulation and biomarker responses in tigerfish, Hydrocynus vittatus. This is because there is relatively little known about the bioaccumulation potential and stress responses of tigerfish to pollutants and they have recently become listed as a protected species. Result from this study showed that there were few differences between seasons in terms of metal bioaccumulation in the Pongolapoort Dam with the exception of Se, Zn and Fe. Selenium and Fe concentrations were linked to concentrations found in the environment, whereas Zn was attributed to a disruption in homeostasis within the fish. Increases in MT were found during the winter months and were attributed to increased metal concentrations at this time, namely Zn and Se, whereas decreases in CEA and PC were observed at this time and were linked to depleted energy reserves, stress and a reduction in the presence of pesticides as a result of decreased runoff during the winter months. It was found in the Olifants and Luvuvhu Rivers that there were no distinct decreases in metal concentrations as the rivers flowed through the KNP, and processes such as rainfall, remobilization of sediments, distance of the study area from the source and geology played a great role in the distribution of metals. Metal concentrations in the Olifants River water, sediment and fish were, for the most part, found to be lower than previous studies, possibly due to improvement in management strategies or increased buffering of this river. Only Al and As were significantly higher in tigerfish from the Olifants River, and this was reflected in high MT concentrations. It was suggested that tigerfish from the Olifants River have developed effective mechanisms for the excretion and detoxification of heavy metals that they are exposed to as a result of extended exposure. Concentrations of AChE were also significantly inhibited in tigerfish from the Olifants River which is indicative of greater concentrations of organophosphates and carbamate pesticides than the other sites. Tigerfish from the Pongolapoort Dam had signifcantly higher levels of MT and significantly inhibited concentrations of AChE in comparison to tigerfish from the Luvuvhu River. The tigerfish from the Luvuvhu River had significantly higher concentrations of Se in muscle tissue. Tigerfish from the Luvuvhu River, also experienced stress as a result of pollution as was apparent from significantly depleted energy reserves in comparison to the other sites under study, and higher concentrations of PC and CYP1A which are typical biomarkers responding to halogenated and aromatic pesticides, such as deltamethrin and endosulfan. It was recommended that further studies be done to assess the presence of pesticides within these systems to determine the contribution of these pollutants to the state of tigerfish

Ph.D. / An investigation was made into the physical, chemical and biological conditions of the Elsburgspruit to establish the extent and quality of pollution over a period of two and a half years from January 1987 June 1989. The results obtained during the investigation can be summarised as follows. Serious faecal pollution as reflected by faecal coliforms, faecal streptococci and coliphage organisms occurs over a large stretch of the river, posing a health risk to the people using the recreational area at' Vosloosrust, downstream from the Elsburgspruit near Kathlehong. The occurrence and large numbers of coliphage organisms occurring at certain sampling localities suggest the possible presence of the pathogenic viruses Salmonella, Pseudomonas and Candida. Effluent and seepage waters from mining areas, discharged into the Elsburgspruit were found to be low in pH and high in concentrations of certain metals such as zinc, manganese and iron. Due to the large volume of this particular effluent, the effects thereof on the water quality and fauna of the streams are felt over a distance of more than seven kilometres. As a result, the recovery of the stream from pollution is severely retarded. A number of species of the numerically dominant aquatic and semi-aquatic macrophytes which occurred within the flood-plain of the Elsburgspruit, were found to be able to absorb and to accumulate substantial concentrations of the various heavy metals, directly from the water, or from adjacent moist soils. It was also found that the Spanish reed, Arundo donax, which covers a large area of the wetland region of the Elsburgspruit in its lower section, absorbed and accumulated substantial quantities of the different heavy metals from the water of the stream. A comparison was made of the extent to which metals are deposited into the sediment under both acidic and alkaline conditions...