Aucune étude physicochimique majeure des eaux du fleuve Chari n’a été réalisée malgré le fait que depuis l’indépendance du Tchad (1960), quelques usines agroalimentaires, des hôpitaux, des usines textiles, des abattoirs… se soient installés sur ses rives. Les résultats des analyses obtenus après un suivi de 2008 à 2010 ont montré la présence des métaux traces dans le Chari. Sur l’ensemble des échantillonnages d’eau analysés, le fer est l’élément métallique majeur devant le manganèse, le zinc et le nickel. Ces résultats varient en fonction des périodes de prélèvement (saison des pluies ou saison sèche). La plupart des valeurs obtenues dépassent largement les seuils acceptables selon les recommandations de l’OMS. La présence des métaux traces dans le Chari résulte aussi bien du processus naturel que de l’activité humaine. Bien que les concentrations de Ni, Cr, Co, Mn et Zn ne soient pas aussi élevées que celle du fer, le profil de répartition de ces éléments entre les différents sites montre une certaine similarité. Les valeurs moyennes de pH indiquent que les effluents ont un caractère légèrement alcalin, tandis que celles relatives à l’oxygène dissous sont satisfaisantes. De ce fait, les eaux du Chari sont impropres, du point de vue physicochimique voire potentiellement dangereuse pour la santé environnementale et humaine. La lutte contre les pollutions doit être entreprise le plus précocement possible / No physicochemical major study of water of the Chari river was carried out in spite of the fact that since the independence of Chad (1960), some food agro factories, hospitals, textile factories, slaughter-houses… were installed on its banks. Also, this work aims to the “contribution to the analytical study of the pollutants (particularly heavy metals) in waters of the Chari river crossing the town of N’Djamena” using the suitable chemical techniques. The results of the analyses obtains after a follow-up from 2008 to 2010 showed the presence of trace metals in the Chari river. On the whole of analyzed water samplings, iron is the major metal element in front of manganese, zinc and nickel. These results vary according to the periods of taking away( rainy season or dry season). The majority of the values obtained largely exceed the acceptable thresholds according to recommendations of WHO. The presence of trace metals in the Chari river results as well from the natural process as of human activity. Although the concentrations of Ni, Cr, Co, Mn, Cu and Zn are not as high as those of iron, the profile of distribution of these elements between the various sites shows a certain similarity. The average values of pH indicate that the effluents are slightly alkaline, while those relating to dissolved oxygen are satisfactory. So the waters of Chari are unsuitable, from the physicochemical point of view, even potentially dangerous for environmental and human health. The control of pollution must be undertaken the most preciously as possible

Les travaux de cette thèse sont consacrés principalement à l'optimisation d'une méthode de remédiation électrocinétique (EK) comme une technologie appropriée pour le traitement de sédiments de dragage de faible perméabilité hydraulique et multi-contaminés (en éléments traces (ET), hydrocarbures aromatiques polycycliques (HAP) et polychlorobiphényles (PCB)). Cette étude porte également sur l’effet du traitement EK sur l’évolution de la toxicité des sédiments. Après une revue bibliographique, une seconde partie a été dédiée aux méthodes d’analyse des contaminants, avec un focus sur leur extraction de la matrice sédimentaire ; ainsi, une nouvelle méthode d’extraction par dispersion de la matrice solide (MSPD) a été développée, pour une extraction rapide et simultanée des HAP et de PCB et une purification de l’échantillon, qui s’est avérée plus efficace que la méthode d’extraction assistée par micro-ondes (MAE). Plusieurs études expérimentales (à différentes échelles) de remédiation électrocinétique ont été décrites dans une troisième partie ; ces études ont été menées sur un sédiment reconstitué ou des sédiments de dragage portuaire. De nombreuses combinaisons de tensioactifs et d’agents chélatants ont été testées comme agents d’amélioration pour abaisser simultanément la concentration en métaux (Cd, Cr, Cu, Pb, Zn) et des HAP/PCB. Le choix a été effectué en raison notamment de leur faible toxicité potentielle, en vue de pouvoir les appliquer ultérieurement pour une restauration sur site : (bio)surfactants (Rhamnolipides, Saponine et Tween 20) combinés avec des agents chélatants (acide citrique (CA) et EDDS). Les résultats obtenus montrent que les métaux (à l'exception de Cr) sont difficiles à extraire de ces sédiments de dragage portuaire à caractère réducteur, qui présentent une capacité tampon élevée, une perméabilité hydraulique très faible et une teneur en matière organique élevée. En revanche, les HAP et les PCB fournissent de meilleurs taux d'abattement (29,2% et 50,2%, respectivement). Dans une quatrième partie, l'efficacité du procédé EK a également été évaluée à travers l’évolution de la toxicité aiguë des sédiments traités sur les copépodes E. affinis exposés aux élutriats de sédiments. Les résultats ont montré que l'utilisation de CA,des biosurfactants et du Tween 20 n'a pas eu d'impact significatif sur la toxicité des sédiments traités. Cependant, les copépodes E. affinis étaient sensibles aux faibles valeurs de pH et aux conditions très oxydantes, ainsi qu’à la présence de Cu et, dans une moindre mesure, de Pb, à condition toutefois qu’ils soient rendus plus mobiles et biodisponibles. En revanche, la toxicité a été peu et même négativement corrélée aux concentrations des HAP et des PCB après le traitement EK, probablement en raison de la production de métabolites oxydés des HAP et des PCB, plus toxiques que les composés natifs. / This thesis research is mainly devoted to the optimization of an electrokinetic (EK) remediation process as a promising technology for treating multi-contaminated (trace metals, polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyles (PCBs)) dredged harbor sediments of low permeability. This study is also investigating the effect of the EK treatment on the evolution of sediment toxicity. After a bibliographic review, asecond part of this study was dedicated to the analytical methods carried out for the characterization of the sediment and its contaminants, particularly to their extraction from the sediment matrix; thus a new extraction method, through matrix solid phase dispersion (MSPD) was developed, for a fast and simultaneous extraction of both PAHs and PCBs, and a sample purification.MSPD appeared more efficient than the microwave assisted extraction (MAE) method. Thereafter many EK experiments (at different scales) were described in a third part. EK remediation tests were performed using a spiked model sediment or natural harbor dredged sediments. Many combinations of surfactants and chelators were tested as EK enhancing agents for decreasing simultaneously metal (Cd, Cr, Cu, Pb, Zn) and PAH/PCB levels. Their choice was done because of their possible low toxicity with a view to use them for future site restoration: (bio)surfactants (rhamnolipids, saponin and Tween 20) combined with chelators (citric acid (CA) and EDDS). The results showed that metals (except Cr) were difficult to remove from this kind of dredged sediment owing to its reductive character, to its high buffering capacity, to its very low hydraulic permeability and to its high organic matter content. However PAHs and PCBs showed better removal levels (29.2% and 50.2%, respectively). In a fourth part, the efficiency of the EK process was also assessed by measuring the evolution of the acute toxicity of the treated sediment on E. affinis copepods exposed to sediment elutriates. The results showed that using CA, biosurfactants or Tween 20 as enhancing agents did not significantly impact the toxicity of the treated sediment. However, E. affinis copepods were significantly sensitive to low pH values and oxidative conditions, to Cu, and to a lesser extent to Pb amounts, if they were transformed in more mobile and bioavailable forms. In contrast, acute toxicity was only slightly and even negatively correlated to PAH and PCB amounts after EK treatment, probably due to the production of oxidized metabolites of PAHs and PCBs, more toxic than the parent compounds.

No description available.

No description available.

Shrinking alpine glaciers alter the geochemistry of sensitive mountain streams by exposing reactive freshly-weathered bedrock and releasing decades of atmospherically-deposited trace elements from glacier ice. Changes in the timing and quantity of glacial melt also affect discharge and temperature of alpine streams. To investigate the effects of glacier ice melt on the geochemistry and hydrology of proglacial streams in the arid Intermountain West, we sampled supraglacial meltwaters and proglacial streams in the Dinwoody Creek watershed in the Wind River Range, Wyoming during late summer 2015, when the contributions of glacier meltwater were highest. Supraglacial meltwater was enriched in 8 trace elements (Cd, Co, Cu, MeHg, Mn, Pb, THg, Zn) relative to proglacial meltwaters. Concentrations of major ions (Mg2+, K+, Na+, Ca2+, SO42-) and the remaining 30+ analyzed trace elements were enriched in proglacial streams relative to supraglacial meltwater. To evaluate the diurnal effects of glacial meltwater on the chemistry and hydrology of proglacial streams, we collected hourly water samples of Dinwoody Creek and deployed loggers to monitor water depth, temperature, and specific conductance (SPC) at 15-min intervals over a 1-week period. The influx of glacial meltwater between 10:00 and 20:00 diluted solute concentrations and affected the relative enrichment/depletion of highly soluble elements (major ions, alkaline earth elements), less than REEs. Stable isotopes of H and O (δD, δ18O) in Dinwoody Creek were more depleted during peak runoff (10:00 – 20:00) than base flow, reflecting contributions from isotopically depleted glacial meltwaters. Looping hysteresis patterns were observed between water depth versus DO, pH, temperature and SPC in glaciated streams. Hysteresis patterns were affected by changes in weather and varied depending on the type of stream (glaciated versus non-glaciated) and the distance to glacier toe. Combination of multiple hydrologic tracers (solute concentrations, high frequency logger data, stable isotopes) shows strong potential to improve estimates of glacial meltwater contributions to Dinwoody Creek. Our results suggest that elevated concentrations of heavy metals in glacier ice melt across the Intermountain West may negatively impact sensitive alpine streams.

[pt] A presença de metais-traço nos cigarros oferece uma fonte de informação potencial do ponto de vista forense e criminológico, na determinação e classificação de marcas de tabaco, com o intuito de diferenciar as marcas legalizadas das contrabandeadas. Por isso, neste trabalho, almejou-se desenvolver e validar métodos para determinação metais e semimetais presentes nos cigarros, com o intuito de avaliar a viabilidade de discriminação entre as diferentes marcas, analisando as amostras após o processo de calcinação e dissolução ácida. Estes métodos englobam as análises químicas por técnicas espectrométricas (CV-AAS, ICP-OES e DRC-ICP-MS) e posterior interpretação de dados por ACP (Análise dos Componentes Principais) e AAH (Análise de Agrupamento Hierárquico). As concentrações de metais e semimetais (As, Ba, B, Cd, Co, Cu, Fe, Mn, Hg, Ni, Sr e Zn) foram estudadas para dez diferentes marcas de cigarros, obtidas em tabacarias e lojas locais, representando as marcas mais consumidas no país. A utilização da ACP indicou a presença de quatro componentes principais que, em conjunto, explicavam mais de 80 por cento da variabilidade dos dados amostrais. Esses resultados comprovaram a existência de diferenças significativas entre as marcas de tabaco em seus conteúdos elementares, possibilitando a diferenciação entre marcas ilegais e marcas legalizadas e o agrupamento das marcas legalizadas de acordo com as empresas de tabaco as quais pertencem, sendo corroborado pela AAH, feita pelo método da distância média de ligação (UPGMA). Os teores de umidade, cinzas totais e pH de cada marca também foram determinados, no entanto não contribuíram efetivamente para a diferenciação entre as marcas estudadas. A AAH foi utilizada para a interpretação de possíveis similaridades entre os elementos, e em conjunto com o teste de correlação linear de Pearson, indicou similaridades entre os elementos Ba e Sr . Agrupamentos entre Fe e Zn com o Sr e Co com o Mn também foram detectados. / [en] The presence of trace metals in cigarettes offers potential source of information from a forensic and criminological point of view, which deals with the determination and classification of tobacco brands, with the aim of differentiating legal brands from smuggled brands. Therefore, this work aimed to develop and validate methods for determining the metallic content present in cigarettes, in order to assess the feasibility of discrimination between different brands, analyzing cigarettes after the process of calcination and acid digestion. These methods include chemical analysis by spectrometric techniques (CV-AAS, ICP-OES and DRC-ICPMS) and subsequent data interpretation by PCA (Principal Component Analysis) and HCA (Hierarchical Cluster Analysis). The concentration of metals and semimetals (As, Ba, B, Cd, Co, Cu, Fe, Mn, Hg Ni, Sr and Zn) were studied for ten different brands of cigarettes, obtained in tobacconists and local stores, representing the brands most consumed in the country. The analysis of PCA indicated the presence of four principal components that together explained more than 80 percent of the variability of the sample data. These results proved the existence of significant differences between tobacco brands in their elemental content, allowing the differentiation between illegal brands and legalized brands and the grouping of legal brands according to the tobacco companies to which they belong, being corroborated by the HCA performed by the average link distance method (UPGMA). The moisture content, total ash and pH of each brand were also determined, however they did not contribute effectively to the differentiation between the brands studied. The HCA used for the interpretation of possible similarities between the elements, and interpreted together with Pearson s linear correlation test indicated similarities between the elements Ba, Sr, in addition to indicating the proximity between the Mn and the Cd. Clusters between Fe and Zn with Sr and Co with Mn were also detected.

Thesis (PhD (Soil Science))--University of Stellenbosch, 2007. / Trace elements occur naturally in soils, usually at low concentrations (<0.1% or <1000 mg kg-1 of the earth’s crust), as a result of weathering and pedogenic processes acting on the rock fragments from which soil develops (parent material). Since about 98% of human food is produced on land, soil is the primary source supplying these elements to the food chain. Although cases of trace element deficiency and toxicity have been documented in many parts of South Africa, no comprehensive description of trace element concentration has yet been attempted for South Africa as a whole. The Natural Resources Land Type mapping project, initiated in the mid-1970s, has provided a collection of samples (approximately 4500) from soil profiles selected to represent the main soil forms in each land type and therefore to provide representative coverage of most of the soils of South Africa. These archived samples have now been analysed for a spectrum of trace elements, in terms of both available and total concentrations as well as other soil properties. Although detailed information is available on a wide range of trace metals, the seven trace metals considered to be of most interest in a South African context due to natural geological occurrences were selected for this study, including Cd, Co, Cr, Cu, Pb, Ni and Zn. This data was used to: • determine baseline concentrations in SA soils; • determining threshold values for South African agricultural soils receiving sewage sludge at agronomic rates; • determining the influence of certain soil properties on the baseline concentrations of these trace elements in SA soils; and • development of a bioavailable trace element distribution map for SA. The range, the mean and standard deviation (both arithmetic and geometric), and the median were used to summarize the data statistically. The baseline concentration range was calculated using the quotient and product of the geometric mean and the square of the geometric standard deviation, including data below the instrument detection limit. The upper limit of the baseline concentration range was set at the 0.975 percentile value of the population in order to minimize the influence of contamination and the lower limit at the 0.025 percentile value to minimize problems that might be associated with analytical uncertainty near the lower limit of detection. The quantile regression statistical approach was followed to illustrate the relationship between soil properties and trace element concentrations in soils. The soil properties that showed the strongest relation were CEC, clay content, pH (H2O) and S value (base status). The soils were then divided into different classes according to these soil properties and baseline concentrations were derived for the different classes. Soils with low clay contents have lower trace element concentrations than soils with higher clay contents, soils with low or high pH levels have lower trace element contents than soils with intermediate pH values and mesotrophic soils have higher trace element concentrations than dystrophic soils. This information is useful for the compilation of trace element distribution maps for South Africa where different soil forms and series/families could be classified into different classes to determine areas of potential deficiencies as well as toxicities. South Africa, with its diverse geology, has areas of both trace element toxicities and deficiencies and for decision-making purposes it is necessary to identify these areas. Mapping of trace element levels based on soil samples would provide valuable information, which cannot be obtained from geological or geographical maps. Statistical analyses of the data (clay %, base status, pH (H2O) and NH4EDTA extractable trace element concentrations) indicated that soils could be divided into five trace element classes based on their clay content, pH and base status (dystrophic, mesotrophic and eutrophic). The soil series according to the binomial soil classification system for South Africa were then divided into these different classes. The geometric means for each clay class were determined and the baseline concentration range for each class was calculated. The land type maps were used as basis for the distribution maps. A general trace element distribution map for South Africa was derived from this data as well as Cu and Zn distribution maps. A random selection of 500 soil samples across the country was used to verify the accuracy of the distribution map. The general trace element distribution map indicate, with a confidence level between 89 and 96%, where the potentially available trace element content of South African soils are low (deficient) too moderately high, excluding rocky areas and areas with limited soil. The Cu and Zn maps indicate the distribution and expected baseline concentrations of these specific elements in South African soils. The same methodology could be applied to derive risk maps for all the individual trace elements to indicate the distribution and expected baseline concentrations of the elements in South Africa. This presentation of baseline concentrations, reflecting likely natural ranges in South African soils, is the first quantitative report on the spatial extent and intensity of Zn, Cu and Co deficiency in South African soils. The proposal of new threshold values for trace elements in agricultural soils will be valuable in setting more realistic norms for environmental contamination that accommodate the geochemical peculiarities of the region, one example being rather high Cr and Ni concentrations with low bio-availability. This information should be of value not only in environmental pollution studies but also in health, agriculture, forestry and wildlife management. The following recommendations are made: • The baseline concentrations could be used to determine site specific threshold values based on soil properties and soil type. Soils with lower pH, clay content and CEC would require more protection than soils with high pH, clay content and CEC and therefore the threshold levels for these soils should be lower. • Although the distribution maps can be used to indicate broad areas of trace element deficiencies and toxicities, more detailed investigations are recommended for areas where problems are experienced. The same methodology could be applied on smaller scale to increase the value of the map and to add more value on a regional scale. The maps could be used for regional soil quality assessment especially in areas where trace element deficiencies or toxicities could result in negative effects on plants and animals.

La présente étude porte sur l’évaluation d’une méthode d’acquisition de la solution de sol présente à l’interface sol-racine, dans la rhizosphère. Cette interface constitue le lieu privilégié de prise en charge par les plantes des contaminants, tels que les métaux traces. Comme les plantes acquièrent ces éléments à partir de la phase liquide, la solution de sol de la rhizosphère est une composante clé pour déterminer la fraction de métaux traces biodisponibles. La microlysimétrie est la méthode in situ la plus appropriée pour aborder les difficultés liées à l’échelle microscopique de la rhizosphère. Ainsi, dans les études sur la biodisponibilité des métaux traces au niveau de la rhizosphère, les microlysimètres (Rhizon©) gagnent en popularité sans, toutefois, avoir fait l’objet d’études exhaustives. L’objectif de cette étude est donc d’évaluer la capacité de ces microlysimètres à préserver l’intégrité chimique de la solution, tout en optimisant leur utilisation. Pour ce faire, les microlysimètres ont été soumis à une série d’expériences en présence de solutions et de sols, où la quantité de solution prélevée et le comportement des métaux traces (Cd, Cu, Ni, Pb, Zn) ont été étudiés. Les résultats montrent que les microlysimètres fonctionnent de façon optimale lorsque le contenu en eau du sol est au-dessus de la capacité au champ et lorsqu’il y a peu de matière organique et d’argile. Les sols sableux ayant un faible contenu en C organique reproduisent mieux le volume prélevé et la solution sous la capacité au champ peut être récoltée. L’utilisation des microlysimètres dans ces sols est donc optimale. Dans les essais en solution, les microlysimètres ont atteint un équilibre avec la solution après 10 h de prélèvement. En respectant ce délai et les conditions optimales préalablement établies (pH acide et COD élevé), les microlysimètres préservent la composition chimique de la solution. Dans les essais en sol, cet équilibre n’a pas été atteint après dix jours et huit prélèvements. Le contenu en matière organique et l’activité microbienne semblent responsables de la modification des concentrations en métaux au cours de ces prélèvements, notamment, dans l’horizon FH où les microlysimètres performent très mal. En revanche, dans l’horizon B, les concentrations tendent à se stabiliser vers la fin de la série de prélèvements en se rapprochant des valeurs de référence. Bien que des valeurs plus élevées s’observent pour les microlysimètres, leurs concentrations en métaux sont comparables à celles des méthodes de référence (extrait à l’eau, lysimètres de terrain avec et sans tension). En somme, les microlysimètres se comportent généralement mieux dans l’horizon B. Même si leur utilisation est plus optimale dans un sol sableux, cet horizon est privilégié pour de futures études sur le terrain avec les microlysimètres. / This study focuses on evaluating a method of acquiring soil solution in the soil-root interface of the rhizosphere. The liquid phase of the rhizosphere constitutes the main area where plants absorb contaminants like trace metals. Thus the rhizosphere soil solution is key to determine the amount of bioavailable trace metals. Microlysimetry has been described as the most appropriate in situ method to tackle difficulties inherent to the microscopic scale of the rhizosphere. Despite the lack of an exhaustive evaluation of their performance, microlysimeters have gained popularity for in situ studies on the bioavailability of trace metals. The objective of this study was to evaluate the capacity of microlysimeter to preserve the chemical integrity of the soil solution and also to determine their optimum use conditions. To do this, microlysimeter have been submitted to a series of laboratory experiments with solutions and soils. The volume of solution extracted and trace metals (Cd, Cu, Ni, Pb, Zn) behaviour were studied. Results show that microlysimeters work optimally when soil water content is above field capacity and when the amount of clay and organic matter is low. Sandy soils with low organic carbon content have a better reproducibility for extracted volume and soil solution extraction is possible even when soil water content is below field capacity. Using microlysimeters in this soil type is thus optimal. In solution experiments, microlysimeters reached equilibrium with the control solution after ten hours of extraction. In optimal conditions (acidic pH and high DOC) and after this ten hours period, microlysimeters preserve the chemical composition of the solution. In soil experiments, this equilibrium has not been reached after eight samplings throughout ten days. Organic matter content and microbial activity could be responsible for the modification of concentrations of trace metals during sampling. This is especially true for FH horizon where microlysimeters perform poorly. In contrast, the concentrations reach the reference values toward the end of sampling serie in the B horizon and microlysimeters have a better overall performance in this horizon. Although higher values are observed for microlysimeters, trace metals concentrations are comparable to other extraction methods, specifically for the B horizon. Even if their uses are optimized in sandy soil, the B horizon should be privileged for future field studies involving microlysimeters.

Le changement d’occupation des sols contaminés est susceptible de modifier la nature et la quantité des matières organiques du sol (MOS). Les matières organiques sont connues pour avoir un rôle de source trophique pour les organismes des sols et un rôle de ligand vis-à-vis des éléments traces métalliques (ETM) dans les sols contaminés. Des changements de matières organiques dus aux changements d’occupation des sols contaminés peuvent modifier la spéciation des ETM et leur disponibilité. Mais dans ce cas, le rôle de la matière organique dans le déterminisme de la disponibilité des ETM est peu documenté. L’objectif du travail présenté dans cette thèse était de mettre en évidence le rôle des matières organiques dans la disponibilité des ETM, dans le cas de sols agricoles contaminés après un changement de cultures annuelles vers des cultures pérennes à vocation non-alimentaire. Le travail a concerné l’étude de la disponibilité du Cu, Pb, Zn et Cd dans les sols de deux sites différents en texture et en origine de pollution i.e. le site de Metaleurop (Nord de la France) avec des sols limoneux contaminés par des retombées atmosphériques et le site de Pierrelaye (Région Parisienne) avec des sols sableux contaminés par les apports d’eaux usées brutes de la ville de Paris. Le rôle de la matière organique a été étudié en travaillant 1) sur des échantillons de sols sous deux cultures différentes i.e. sous culture annuelle et culture pérenne à vocation énergétique miscanthus depuis trois ans, 2) sur les échantillons de sol avant et après incubation in vitro afin d’accélérer la minéralisation de la matière organique, et 3) sur des échantillons de sol avec et sans matières organiques particulaires (MOP) i.e. les fractions libres des MOS afin de mettre en évidence leur rôle spécifique. Une approche combinée d’évaluation de la disponibilité par des extractions chimiques des ETM et d’étude de la localisation des ETM dans des fractions granulométriques a été utilisée. Les résultats obtenus montrent que l’impact de l’occupation des sols (sous culture annuelle ou pérenne miscanthus) sur la disponibilité des ETM était différent pour les deux sites étudiés. Pour les sols du site de Metaleurop les résultats ont montré que la disponibilité de Cu et Pb diminuait sous miscanthus tandis qu’une augmentation de leur localisation dans les fractions fines était observée. Par contre aucun changement n’a été observé pour Zn ni Cd dans ce site. Au contraire pour les sols sableux riches en matières organiques de Pierrelaye le changement d’occupation a impacté la disponibilité de Zn et Cd tandis que celle de Pb et Cu n’a pas évolué. Les résultats des sols avant et après incubation montrent que l’impact de la minéralisation des MOS sur la disponibilité des ETM était site dépendant pour Pb et Cd alors que l’effet sur Cu et Zn était similaire pour les sols des deux sites. En travaillant sur les sols avec et sans MOP, nous avons pu observer que les MOP en tant que fraction organique libre participaient à la disponibilité des ETM telle qu’étudiée, et que une partie du cuivre lié aux MOP était disponible pour un organisme dans nos conditions. Ces résultats de disponibilités des ETM dans des sols qui varient avec la nature et la quantité des matières organiques sont discutés. / The changes in land use of contaminated agricultural soils are susceptible to modify their trace metal availabilities by changing the quality and quantity of soil organic matter. But the role of soil organic matter in the determinism of trace metal availabilities in contaminated soils is not well known. The objective of the present study was to assess the role of soil organic matter in determinism of trace metal availabilities and their dynamics in contaminated soils varying in their texture and nature of pollution. A strategy of studying Cu, Pb, Zn and Cd availabilities of two sites with different texture and origin of pollution was adopted and the role of organic matter was assessed through; 1) sampling the soils of two parcels at each site with two different land uses i.e. under annual crop and under perennial energy crop miscanthus, 2) changing the soil organic matter of these soils through in vitro soil incubations. A combined approach of chemical metal extractions and metal localization study in different soil size fractions was used. The results of the trace metal availabilities of the soil under miscanthus compared to annual crop soil showed that the influence of changes in organic matter through land use was different at both sites. In the silty clayed soil, the availability of Cu and Pb which are the metals known to be preferentially bound to organic matter was decreased with an increase in their localization in soil finer fractions. In the site with organic matter rich sandy soils the availability of metals which are known to be bound to soil mineral phases i.e. Zn and Cd was changed without a change in their localization. The results of laboratory incubation experiments revealed that the mineralization of soil organic matter affects the trace metal availability in two ways. Cu and Zn availabilities are changed in all soils whatever the texture while Pb and Cd availabilities changed only in sandy soils. This difference of the change of metal availabilities in both cases of organic matter variations i.e. between the soil samples under different land use and in the samples of laboratory incubations can be explained by the fact that the changes in organic matter were not similar in both cases. Our work on the metal enriched particulate organic matter (POM) fractions, the most labile organic matter fractions showed that POM act as source and sink of the metals in our conditions and POM associated copper is bioavailable in liquid medium but its bioavailability is less than the metal added as salt solution. These results, increasing the understanding of the role of soil organic matter in the determinism of trace metal availability in different textured soils, are discussed.

Le Morvan et les Cévennes sont des massifs protégés pour leur paysage et leur biodiversité exceptionnels. Cependant dès la Protohistoire, ces régions réputées pour la qualité de leur environnement ont été le lieu d’activités minières et métallurgiques. Les effets de telles activités peuvent être rémanents sur les écosystèmes, il est donc important dans un premier temps de les localiser, puis de quantifier leur impact sur la faune et la flore. Le présent travail propose une démarche pluridisciplinaire alliant archéologie, géochimie, écologie et écotoxicologie. L’application de méthodes statistiques empruntées à la prospection minière a permis de dresser des cartes de potentiel minier, supposées guider l’archéologue dans ses recherches de terrain. Des cartes de distribution spatiale des éléments traces métalliques ont été construites sur six sites (trois dans chaque parc). La biodisponibilité des éléments traces métalliques a été estimée sur des mulots, des truites et des bryophytes. Bien que la plupart de ces éléments semblent appartenir à la fraction non-extractible des sols, la part biodisponible restante peut être détectée dans des bioindicateurs. Une relation négative entre les indices de condition et la concentration en plomb dans les animaux, et dans certains cas une plus grande instabilité de développement a été trouvée, suggérant la présence d’effets délétères sur les organismes. L’impact des anciens sites miniers et métallurgiques est donc toujours décelable dans les écosystèmes actuels. Ces sites doivent être surveillés, notamment au sein des zones protégées supposées à tort comme éloignées de toutes contaminations anthropiques. / The Morvan and the Cevennes Massifs are nowadays protected for their outstanding landscape and biodiversity. However since Prehistory, these regions experienced mining and smelting activities. Because of remnant properties, locating these ancient sites is capital and then impact on fauna and flora must be estimated. This present work is based in on a pluridisciplinary approach combining archeology, geochemistry, ecology and ecotoxicology. Statistical methods, from modern prospection technique, have been applied in order to delineate geochemical anomalies, potentially due to mining exploitation and thus facilitate the archeological prospection. Spatial distribution maps of trace metals were built on six sites (three in each park). Biodisponibility was assessed thanks to the analyses of wood mice, trout and bryophytes. Even if it seems that most of these elements belong to the non-extractible fraction of soil, the remaining bioavailable trace metals can be detected in the bioindicators. A negative relationship between Pb concentrations in animals and their body condition indices was found, and in some cases developmental instability was higher, suggesting deleterious effect on current wildlife. As a consequence, the impact of past mining and smelting works is still traceable in ecosystems. For this reason, these sites should be monitored, particularly in protected areas thought to be relatively free of anthropogenic contamination.