Thèses sur le sujet « Industrial soil pollution »

No Município de Salto - SP, em um Distrito Industrial ocupado por 21 empresas que desenvolvem atividades diversas, estudou-se o comportamento de íons associados ao solo, águas (subterrâneas e superficiais), sedimentos e resíduos descartados. Foi permitida a coleta de materiais em apenas quatro indústrias do Distrito. O solo foi caracterizado quanto aos seus atributos (análises granulométrica, mineralógica e química) e suas propriedades não são favoráveis a fixação de íons. No solo das indústrias foram detectados em elevadas concentrações bário e fluoreto e em menores teores, íons como cádmio, zinco, chumbo, e cobre. No entanto no solo, em uma das indústrias, associado a área de descarte de resíduos industriais detectou-se grande enriquecimento de bário na forma de sulfato que, em função das condições ambientais, pode se tornar disponível ao meio ambiente. As águas subterrâneas, apresentaram teores muito acima dos valores preconizados pela legislação para os íons ferro e manganês. Nas águas superficiais foram detectados íons comuns a toda área, contudo nenhum acima dos recomendados pelos órgãos ambientais. Nos sedimentos de fundo do lago ressalta-se a presença de ferro e alumínio na forma dos minerais hematita e gibbsita confirmada pela coleta de sedimentos nos baldes coletores instalados no lago.
On the Municipality of Salto - SP, on a Industrial District occupied by 21companies that develop various activities, it was studied the behavior of íons associated to the soil, water (underground and surface), sediments and discarded residues. It was allowed the gathering of materials only on four of the District industries. The soil was characterized regarding it\'s attributes (glanurometric analysis, mineralogical and chemical). It\'s properties aren\'t favorable to íon fixation. In the industries soil, elevated concentrations of barium and fluoride were detected, íons as cadmium, zinc, lead and copper were also detected, but on a lesser degree. However in the soil, of one of the industries, associated with the discard area of industrial residues it was detected a high enrichment of barium in the form of sulfate wich, according to the environmental conditions, may become avaliable to the environment. In the underwater the íons of iron and manganese presented themselves on above the recommended levels. In surface water it was detected íons common to the whole area, however none above the recommended by the environmental organs. In the sediments on the botton of the lake stands out the presence of iron and aluminium in the form of hematite and gibbsite minerals. Confirmed by the collecting of sediments in buckets installed in the lake.

Thesis (MSc)--University of Stellenbosch, 2011.
ENGLISH ABSTRACT: Landfarming is a widely used method for the disposal of contaminants in the petrochemical industry. It involves ploughing the contaminants into the top soil layer allowing biological breakdown. A historically landfarmed site was identified at a South African petrol refinery. The refinery used to dispose so-called American Petroleum Institute (API) -sludge onto a landfarming site. API-sludge consisted of a mixture of oil and water soluble contaminants originating from a process of separating refinery waste from reusable water and oil. Landfarming on this site was discontinued after excessive quantities of sludge were ploughed into the soil over time and it became obvious that effective biodegradation could not take place. An environmental assessment had to be carried out to assess to what extent the soil has recovered from the contamination and after remediation was done over time. Bioassays together with chemical analyses were executed to determine the level of pollutants in the soil and to assess the integrated effects of their bioavailable fractions. The landfarming site of the refinery was divided into two sections namely, a more contaminated north-site and less contaminated south-site. Soil samples were collected from both sites as well as from an off-site (control site). The soils were analysed physically, chemically and used in the bioassays. Two additional control soils were also used, OECD-soil and LUFA2.2 soil. Chemical analysis of the site soils showed the presence of heavy metals and high levels of diesel range organic hydrocarbons. The north-site had higher levels of contaminants compared to the south-site. Three species of soil organisms were used in standardised tests: Eisenia andrei, Enchytraeus doerjesi and Folsomia candida were exposed to the respective soils to study their survival, growth, reproduction success and avoidance behavior. Exposures to both site-soils were not acutely toxic to any organisms. F. candida had a decrease in juvenile production in both north- and south-site soils (289.42 ± 58.62 and 253.33 ± 122.94 respectively) compared to the control soil (479.89 ± 30.42). E. doerjesi showed an increase in produced juveniles exposed to north- and south-site soil (339.75 ± 76.92 and 414.00 ± 17.78 ) compared to control soil (57 ± 34.39). E. andrei had similar cocoon production when exposed to south-site soil than in off-site soil (19.00 ± 5.3 and 18.5 ± 9.7 respectively) but significantly less in north-site soil (1.25 ± 0.7). Only E. doerjesi showed avoidance of north-site soil. To determine the sensitivity of the organisms to the API-sludge, they were exposed to concentration series of API-sludge-spiked control soils. The effect concentrations were calculated as the concentration of API-sludge that will decrease the studied endpoints by 50% of the control soil (EC50). The EC50s varied for each species exposed in the different control soils showing that the toxicity of the API-sludge is to a certain extent dependent on the physical soil properties of the substrate. The reproduction of F. candida were most sensitive to the API-sludge in off-site soil (EC50 = 90 mg/kg) and the E. doerjesi the least sensitive in LUFA2.2 soil (EC50 = 36000 mg/kg). Five plant species were exposed to API-sludge-spiked potting soil and the germination success, early growth rate and biomass were studied. The plants were not as sensitive to API-sludge as the soil animals. Lettuce and grass were affected the most by API-sludge and beans were the most resilient species. With the addition of low levels API-sludge to the substrate, the growth rate of beans was stimulated. This study showed that the south-site has been successfully remediated and most soil organisms exposed to these soils were not affected by the levels of toxicants present. However, exposures to north-site soil still had negative effects on soil organisms. It is recommended that hydrocarbon contamination should be further remediated in the north-site soil before landfarming should be allowed to continue.
AFRIKAANSE OPSOMMING: Ploegverwerking is ‘n algemene remediëringsmetode vir die verwerking van afvalmateriaal in petrochemiese industrieë. Dit behels die inploeg van toksiese afvalmateriaal in die boonstegrondlaag sodat dit biologies afgebreek kan word. ‘n Voorbeeld van ‘n histories ploegverwerkte grondstuk is geidentifiseer by ‘n Suid-Afrikaanse olieraffinadery. Die raffinadery het in die verlede van die grondstuk gebruik gemaak om sogenaamde Amerikaanse Petroleum Instituut-slik (API-slik) daarin te ploeg. Die API-slik bestaan uit ‘n mengsel van olie- en wateroplosbare kontaminante afkomstig van die proses waardeur die raffinadery se afvalprodukte van hernubare water en olie geskei word. Nadat oormatige konsentrasies slik in die grond ingewerk is en bioremediasie nie meer doeltreffend kon voortgaan nie, is die ploegverwerking gestaak. ‘n Omgewingimpakstudie moes uitgevoer word om te bepaal tot watter mate die grond herstel het nadat remediasie oor tyd uitgevoer is. Toksisiteitstoetse en chemiese analises is uitgevoer om die vlakke van besoedeling sowel as die biobeskikbare fraksie daarvan in die grond te bepaal. Die ploegverwerkte area van die raffinadery is in twee verdeel naamlik, ‘n meer gekontamineerde noordelike area en ‘n minder gekontamineerde suidelike area. Grondmonsters is van die onderskeie areas asook van ‘n ongekontamineerde veld (as kontrole) naby die ploegverwerkte area versamel Die gronde is fisies- en chemies geanaliseer en toksisiteitstoetse is uitgevoer. Twee addisionele kontolegronde is ook tydens die blootstellings gebruik naamlik, OECD- en LUFA2.2-grond. Die chemiese analises van die ploegverwerkte toetsgronde het getoon dat daar steeds swaarmetale en hoë vlakke van dieselgekoppelde organiese koolwaterstowwe in die gronde teenwoordig is. Kontaminante was in hoër konsentrasies teenwoordig in die grond van die noordelike gebied as in dié van die suidelike gebied. Drie spesies van grondorganismes is gebruik tydens standaard toksisitetitstoetse. Eisenia andrei, Enchytraeus doerjesi en Folsomia candida is blootgestel aan die onderskeie toets- en kontrolegronde waarna hul oorlewing, groei, voortplantingsukses en vermydingsreaksies bestudeer is. Blootstellings aan die ploegverwerkte toetsgronde het geen akute toksisiteit vir enige van die spesies getoon nie. F. candida se juveniele produksie was laer in beide noordelike- en suidelike toetsgronde (289.42 ± 58.62 en 253.33 ± 122.94 onderskeidelik) as in die kontolegrond (479.89 ± 30.42). E. doerjesi blootstellings het ‘n toename in juveniele getalle getoon in die noordelike- en suidelike toetsgronde (339.75 ± 76.92 en 414.00 ± 17.78) in vergelyking met die ongekontamineerde kontolegrond (57 ± 34.39). Kokonproduksie by E. andrei was soorgelyk in die suidelike toetsgrond en ongekontamineerde kontrolegronde (19.00 ± 5.3 en 18.5 ± 9.7 onderskeidelik) maar beduidend minder as in noordelike toetsgrond (1.25 ± 0.7). Slegs E. doerjesi het ‘n beduidende vermydingsreaksie vir die noordelike toetsgronde getoon. Om die sensitiwiteit van die organismes aan vars API-slik te bestudeer, is hulle blootgestel aan konsentrasiereekse van API-slik in die onderskeie kontrolegronde. Die effektiewe konsentrasie (EK50) is bereken as die konsentrasie van API-slik wat die bestudeerde eindpunte met 50% sal verminder in vergelyking met die kontrolegrond Die EK50-waardes vir al die spesies het verskil na blootstelling aan die onderskeie kontrolegronde. Dus, die toksisiteit van die API-slik is tot ‘n sekere mate ook afhanklik van die fisiese grondeienskappe van die blootsellingssubstraat. Die voortplanting van F. candida was die gevoeligste eindpunt vir die blootstelling aan API-slik in kontolegrond (EK50 = 90 mg/kg) en E. doerjesi was die minste gevoelig in LUFA2.2 grond (EK50 = 36000 mg/kg). Vyf plantspesies is ook blootgestel aan API-slikgekontamineerde potgrond en die saadontkiemingssukses, vroeë groeikoers en biomassa is bestudeer. Alhoewel plante nie so sensitief was vir die API-slik soos die gronddiere nie, was blaarslaai en gras die meeste geaffekteer tydens die blootstellings. Boontjies was die ongevoeligste en met die toevoeging van lae konsentrasies API-slik (2.5% API-slik), is hul groeikoers selfs gestimuleer. Uit die studie was dit duidelik dat die suidelike deel van die grondstuk meer suksesvol as die noordelike geremidieer is en dat meeste grondorganismes wat daaraan bloot gestel is nie geaffekteer is deur die vlakke van kontaminasie wat steeds teenwoordig is in die grond nie. Die toetsgronde uit die noordelike deel het egter steeds negatiewe effekte op die grondorganismes gehad. Dit word voorgestel dat die koolwaterstof kontaminasie verder geremidieër behoort te word in die noordelike deel van die grondstuk voordat verdere ploegverwerking van die afval daar gedoen word.

As antigas áreas industriais na cidade de São Paulo têm sofrido uma progressiva perda das suas funções originais, tornando-se objeto de intensas transformações, particularmente no que diz respeito ao reaproveitamento dos imóveis e ao padrão de ocupação do solo existente, mediante a implantação de grandes empreendimentos imobiliários e a introdução de atividades totalmente diversas daquelas que as haviam caracterizado no passado. As formas pregressas de uso dessas áreas tornam possível a ocorrência de contaminação do solo e das águas subterrâneas, o que exige cuidados e procedimentos específicos para o reúso de terrenos ali localizados. Tendo como objeto de estudo a reutilização de antigas áreas industriais em processo de transformação na cidade de São Paulo, a presente tese parte da hipótese principal de que a construção de paisagens pós-industriais, sob a perspectiva da recuperação da função dos espaços urbanos e da garantia das condições de saúde pública e da sustentabilidade ambiental, só pode ser concebida no âmbito de um processo de gerenciamento de áreas contaminadas que contemple as dimensões interdisciplinar e interinstitucional da questão e leve em consideração a participação dos atores envolvidos. Tendo em vista que a reabilitação de áreas contaminadas abrange as dimensões básicas abordadas pelo que se passou a denominar sustentabilidade, a pesquisa teve início com o levantamento das diversas concepções adquiridas pelo termo, assim como das alterações ocorridas nas relações entre homem e natureza e suas implicações sobre as transformações observadas na paisagem ao longo do tempo, por meio de pesquisa bibliográfica. O tratamento dado ao problema das áreas contaminadas foi analisado a partir da forma de atuação fragmentada do poder público, mediante exemplos que demonstram a total ausência de integração entre os seus diferentes setores, e também do levantamento de instrumentos de incentivo à reabilitação de áreas contaminadas e de experiências internacionais sobre o tema. Considera-se, por fim, que além da visão interdisciplinar e interinstitucional, a reabilitação das áreas contaminadas na cidade depende da forma de atuação do poder público e da existência de mecanismos de incentivo.
The old industrial areas in the city of São Paulo have suffered a progressive loss of their former functions, becoming object of intense transformations, particularly concerning the use of the properties and the existing pattern of occupation of the land, through the construction of huge real estate projects and the introduction of activities totally different from those ones which characterized them in the past. The former uses of these areas make possible the occurrence of soil and groundwater contamination, what requires cares and specific procedures to reuse of the sites located in those places. Taking the reutilization of the old industrial areas in process of transformation in the city of São Paulo as the object of study, the present thesis starts from the main hypothesis that the construction of post-industrial landscapes, under the perspective of the urban space function recovery and the guarantee of the health public and the environmental sustainability, can only be conceived within the scope of a contaminated sites management process which satisfies the interdisciplinary and inter-institutional dimensions and takes into account the stakeholders involved in it. Considering that the rehabilitation of contaminated sites covers the basic dimensions treated by what was called sustainability, the research started with the survey of the various conceptions acquired by the term, as well as the changes occurred in the relationship between man and nature and its implications on the transformations of the landscape along the time, by means of bibliographical research. The treatment given to the contaminated sites issue was analyzed from the fragmented way of acting of the public administration, by means of examples which demonstrate the total lack of integration among their different sectors, and also from the survey of incentive instruments for the rehabilitation of contaminated sites and international experiences on the theme. At last, it\'s considered that, beyond the interdisciplinary and inter-institutional view, the rehabilitation of the contaminated areas in the city depends on the way the public sector acts and the existence of incentive mechanisms as well.

Contaminated sites in low prioritized regions demand remediation technologies that are cost- and energy-effective and locally adapted. Parameters such as the time frame during which bioremediation degradation needs to occur may not be as restraining as in urban environments. This licentiate project aims to explore opportunities and constraints for appropriate soil remediation based on organic by-products in tropical developing countries and sparsely populated areas in industrial countries. Ecological Engineering and the Framework for Strategic Sustainable Development were explored as planning tools to steer bioremediation methods towards sustainability. The use of the five concepts of Ecological Engineering within the Framework for Strategic Sustainable Development can steer bioremediation in low prioritized regions towards sustainability. Pilot-scale and laboratory experiments were undertaken to evaluate the feasibility of such bioremediation methods. Experiments carried out at the experiment station in Chontales, Nicaragua showed some promising results, but also revealed problems associated with the clay rich soils, which are typical for tropical regions. Treatment of diesel contaminated ultisol with 6 mL whey kg-1 dw in a pilot-scale experiment considerably increased the degradation rate of diesel constituents, but no effects on the degradation rates were observed after treatment with compost tea or pyroligneous acid.The soil columns study suggests that despite a favorable particle size distribution for microbial transport, the sandy loam retained a greater fraction of the microorganisms present in the ACT in the top 10 cm than the clay loam, presumably because the lower bulk density and higher SOM in the clay loam aided transport and growth of microorganisms.

Du fait des activités industrielles anciennes et du recyclage croissant des produites résiduaires organiques d’origine urbaine dans les sols agricoles, des composés organiques persistants, parmi lesquels les hydrocarbures aromatiques polycycliques (HAP) se retrouvent présents dans les sols français. Dans le cadre de la gestion des sites et sols pollués et de l'évaluation des risques associés aux HAP dans l'environnement, une meilleure connaissance du comportement, de la dissipation, du transfert ou de l’accumulation des HAP dans les sols est alors indispensable. Dans ce but, il est utile de développer une nouvelle génération de modèles numériques basés sur le couplage flexible de l’ensemble des processus majeurs contrôlant la dynamique des HAP dans le sol. Notre travail repose sur la mise en œuvre, dans le cadre de la plateforme VSoil de l’INRA (https://www6.inra.fr/vsoil/The-Project), d'un modèle global interdisciplinaire de dynamique des HAP dans les sols, applicable à l’échelle du terrain et couplant des modules décrivant les principaux processus physiques, biochimiques et biologiques. Ce modèle associe d’une part des modules déjà publiés simulant la décomposition des matières organiques exogènes apportées, le transfert d'eau, le transfert de chaleur et le transport de solutés dans des conditions climatiques réelles, et d’autre part, un nouveau modèle représentant spécifiquement la réactivité des HAP.La démarche numérique adoptée dans ce travail a alors été de i) calibrer le modèle de terrain en utilisant des paramètres déterminés à partir de données expérimentales obtenues au laboratoire et complétées avec une partie des données de terrain obtenues sur une courte période, ii) tester et valider le modèle calibré au terrain à l'aide des données de terrain complémentaires sur des périodes plus longues, iii) tester différentes hypothèses de variation de disponibilité et scenarios climatiques ou d’apports répétés de différents composts sur le devenir de HAP dans le sol. Nos résultats montrent que le modèle peut prédire de manière satisfaisante le devenir des HAP dans le sol sur une gamme de contamination allant de parcelles agricoles amendées avec des matières organiques faiblement contaminées jusqu’à d’anciens sites industriels fortement contaminés et permettent alors de mieux appréhender les processus contrôlant la dynamique des HAP dans ces différents systèmes
Due to former industrial activities and the increasing recycling of organic waste products from urban areas in agricultural soils, increasing amounts of persistent organic compounds, among them polycyclic aromatic hydrocarbons (PAH), are to be found in French soils. In the framework of the management of polluted sites and soils and the risk assessment of PAH transfer in the environment, it is essential to better understand the behavior, dissipation, transfer or accumulation of PAH in soils. For this purpose, there is a need to develop a new generation of numerical models based on the flexible coupling between the processes describing PAH dynamics in soil. Our work presents the development and assessment of such model. It is based on the implementation of an interdisciplinary global model, and applicable at the field scale, for PAH in soil by coupling modules describing the major physical, biochemical and biological processes influencing the fate of PAH in soil, with modules that simulate water transfer, heat transfer, solute transport, and organic matter transformation under real climatic conditions. The coupling is performed using the «VSoil» modeling platform of INRA (https://www6.inra.fr/vsoil/The-Project). The steps of our modelling study are the following: i) calibrate the model at the field scale using previously estimated parameters at the lab-scale and completed with field data on a short period of time, ii) test and validate the calibrated model using field experimental data on mid term periods, iii) test different hypotheses of variation of availability and climatic scenarios or repeated applications of different composts on the fate of PAH in soil. Our results show that the model can adequately predict the fate of PAH in soil over a wide range of contamination ranging from agricultural plots amended with weakly contaminated composted organic wastes to old industrial sites heavily contaminated. This new tool allows, therefore, a better understanding of the processes controlling the dynamics of PAH in these different systems

The remediation of two contaminated soils in the Tyne and Wear Metropolitan district was examined. These were a sediment dredged from the river bed at Dunston Coal Staiths on the River Tyne (downstream from Derwenthaugh coke work site) and coke work-contaminated soil from the Derwenthaugh site, Blaydon, Nr. Newcastle-upon-Tyne. The river Tyne dredgings were of a very fine material (70% silt; 24% clay) with high water retention capacity. Levels of (EDTA available) Zn (490mg/kg), total Cd (7.5mg/kg) and total Pb (510mg/kg) were above the Department of Environment's (1987) threshold values for soil contaminants. Barley (Hordeuin vulgare L. cv Kym) sown in the drcdgings in ten outdoor plots (Irn x 0.5m), grew very poorly (yield = 2.4g dry wt. /plant, compared with that on an uncontaminatedc. ontrol soil (7.4g dry wt./ plant). The barley exhibited all the classic signs of metal phytotoxicity despite the addition of fcrtiliscr and organic waste (straw and spent mushroom compost). When lime was added to raise the pH of the dredgings in the plots to over pH 7.1, the growth rate and the yield of barley improved significantly (yield = 6.8g dry wt. /plant). Levels of available Zn, Cd, Pb and Cu in the limed dredgings were now lower than in the unlimed dredgings. Copper and zinc levels in leaves of barley raised on the limed material were lower than levels in barley grown on unlimed dredgings. There was no significant difference in yield or growth rate between the different plots of dredgings in which organic supplementation parameters were varied. In conclusion, pH was the dominant factor in the remediation of the heavy metal phytotoxicity in the dredged material. Gas chromatography/mass spectrophotometry analysis showed the principal contaminants of the coke works soil to be organic. The soil was heavily contaminated with coal tars (19.0%) consisting of a complex mixture of aliphatic, polycyclic and aromatic compounds including phenols (160mg/kg). Viable counts of the soil microflora, on selective media, showed the presence of bacteria capable of degrading phenol and several of its alkylated homologues and thiocyanate, which was converted to ammonia and used as aN source. The coke works soil was treated on a laboratory scale using microbially based clean-up methods. Soil was incubated in glass jars under laboratory conditions. Nu trients (yeast extract) and microbial biomass (a mixed culture, previously isolated and enriched by growth on cresol and thiocyanate, but capable of oxidising a wide range of alkylated phenols), were inoculated into the contaminated soil. The addition of such biomass (106 organisms /g soil) led to a marked improvement in the rate of phenolic degradation in the soil (26% loss in'22 weeks, compared with 9% in the untreated control. ). Degradation rates decreased after 14 days but a repeated application of biomass (106 organisms/g soil) caused further phenolic loss (47% total loss). Cresol (100mg/kg) subsequently added to the bacterial ly-amended soil disappeared within 7 days, showing that the biomass amendment was still biochemically very active. These findings demonstrate the importance and the effectiveness of two different treatment methods in the rcmediation of contaminated soil.

Les potentiels de nouveaux moyens d’investigation en sciences de l’environnement, tel que la géochimie des isotopes stables du Cu et du Zn et l’étude de la spéciation des éléments en trace métalliques (ETM) par titrage acidimétrique sont évalués dans le cadre de trois cas d’études, faisant intervenir des matériaux de matrices et de concentrations en ETM variables. Afin de mettre en évidence de très subtiles variations des compositions isotopiques du Cu et du Zn dans les matériaux particulaires variablement pollués, une attention particulière à été voué à la mise au point des méthodes de séparation chimique et d’analyse par MC-ICP-MS. La méthodologie analytique a été développée afin d’exploiter tout les avantages techniques offerts par le spectromètre de masse à l’ULB. Différents modes d’introduction (plasma humide vs plasma sec (Aridus/DSN), d’acquisition des mesures (mode statique ou dynamique) de correction du biais de masse (dopage au Cu, au Zn et au Ga; correction SSBM, SSBC et EEN)ont été évaluées, pour leurs effets sur la précision et la reproductibilité des mesures. D’autres travaux ont permis de quantifier les effets des interférences spectrales et non spectrales par les éléments de la matrice (Ti, Cr, Co,Fe, Ba, Si, Na, Mg et Ca)et par le rapport dopant/analyte en vue de comprendre les sources d’inexactitudes des mesures isotopiques et d’y remédier. Les données isotopiques acquises sur des minerais, sur des (plaques de) dépôts atmosphériques (usine Pb-Zn Metaleurop de Noyelles-Godault), sur des sédiments et des matières en suspension (estuaire de l’Escaut et mer du Nord), révèlent des variations significatives des compositions isotopiques du cuivre et du zinc. Dans l’estuaire de l’Escaut, les variations temporelles (carotte non perturbée, enregistrant la sédimentation sur 30 ans) et spatiales (matières en suspension échantillonnées sur 100 km, selon le profil de salinité) sont caractérisées par des signatures isotopiques en Zn anticorrélées à celle du Cu. Les données peuvent permettre de distinguer le fond géochimique naturel (le « réservoir naturel »), les pollutions diffuses (le « réservoir anthropique commun »- intégrant de multiples sources de contamination en provenance du bassin versant) et certaines pollutions ponctuelles associées à la métallurgie du Zn. Alors que les procédés utilisés en métallurgie sont eux,capable de produire des signatures isotopiques très fractionnées en Zn, ni la diagenèse précoce dans les sédiments, ni les gradients physicochimiques développés lors du mélange des eaux continentales et marines ne sont capables d’affecter significativement la signature isotopique du Cu et du Zn en phase particulaire. Dans de tels milieux, les signatures isotopiques en Cu et Zn (ainsi que celles en Pb) semblent n’être contrôlées que par le mélange conservatif entre le « réservoir naturel » et le « réservoir anthropique commun ». Les données en elles-mêmes constituent la seule base de données isotopiques en Cu, Zn, Pb dans des matériaux particulaires anthropisés estuariens et marins jamais produite à ce jour. Elles permettent de prédire que la signature isotopique en Cu du « réservoir naturel » devrait être légèrement plus enrichie en isotopes lourds que celle du réservoir « anthropique commun » (par analogie au Zn).

Si la géochimie isotopique du Cu et du Zn a le potentiel de distinguer différentes sources de pollution, l’évaluation des risques liés à ces pollutions doit tenir compte des formes chimiques des ETM, typiquement mises en évidences par les méthodes d’extraction sélectives (séquentielles, dont le protocole BCR). La méthode alternative proposée pour l’étude de la spéciation, plus versatile (capable de mettre en évidence des phases non prédéfinies et applicable à une variété de matrices plus large) est capable de surmonter plusieurs limitations (dont les problèmes de sélectivité liées au mauvais contrôle de l’acidité du milieu réactionnel) caractéristiques des méthodes traditionnelles. Appliquée à des sédiments marins/estuariens et des sols, la méthode de titrage acidimétrique s’est révélée capable de quantifier les proportions relatives des phases acido-solubles (principal problème des méthodes d’extraction sélectives), ce qui permet d’établir univoquement la spéciation des éléments qui leurs sont associés, d’évaluer la réactivité des ETM vis-à-vis du pH, mais aussi d’évaluer la sélectivité des protocoles d’extraction séquentielle « BCR » et « Tessier ». La méthode de titrage acidimétrique apporte également des informations importantes sur la géochimie des éléments majeurs dans l’estuaire de l’Escaut et met en évidence les particularités minéralogiques des sols pollués en comparaison aux sédiments.

Les études de cas démontrent que ces nouvelles techniques ont des applications dans le domaine de la géochimie de l’environnement, mais peuvent également être vouées, sur le moyen/long terme à une utilisation sortant du cadre des sciences exactes. En effet, l’identification/discrimination des sources de pollutions et l’évaluation des risques de remobilisation des polluants métalliques font partie des nombreuses questions posées par la société aux scientifiques de l’environnement.
Doctorat en Sciences
info:eu-repo/semantics/nonPublished

À l’heure actuelle, la contamination des sols est une problématique majeure. En France, un peu plus de 10 045 sites et sols pollués ont été recensés à la mi-2022. D’après une étude de 2018, les hydrocarbures aromatiques polycycliques (HAP) et les éléments traces métalliques (ETM) étaient responsables de cette pollution à hauteur de 14% et 23%, respectivement. La pollution des sols a un impact significatif sur la biodiversité des écosystèmes et la santé humaine. Dans le cadre des politiques d’urbanisation et d’une « zéro artificialisation nette » des sols, la restauration des friches industrielles présente un grand interêt, mais la dépollution de sols co-contaminés en HAP et ETM reste un défi. La mycoremédiation, procédé utilisant les capacités naturelles de souches fongiques afin d’éliminer ou de transformer certains polluants présents dans une matrice environnementale, suscite un intérêt grandissant de par la résistance de certaines souches fongiques à la co-contamination et à leur capacité à coloniser les sols par leur réseau mycélien. Ces travaux de thèse ont permis d’amorcer le développement de nouveaux outils analytiques pour l’analyse des HAP et de certains métabolites oxygénés (cétones, quinones, hydroxylés) de manière semi-automatisée par thermodésorption couplée à la GC-MS/MS en tandem. Une nouvelle méthode, utilisant un polymère de cyclodextrine, a été appliquée pour évaluer la bioaccessibilité des HAP dans le sol industriel d’étude. Une étude en microcosmes de sol d’une durée de 6 mois a permis d’exclure l’utilisation de la souche modèle Absidia cylindrospora pour la mycoremédiation du sol étudié : les fortes concentrations et disponibilités de certains ETM (Pb, Cu, Zn), la très faible bioaccessibilité des HAP, n’ont pas permis à la souche fongique de contribuer significativement à la biodégradation des HAP. De nouvelles souches fongiques ont été isolées à partir du sol industriel. Une souche indigène de Penicillium annulatum résistante aux Cu, Pb et Zn et capable de biodégrader les HAP a été sélectionnée pour une étude à plus grande échelle, en bac pouvant contenir 2 kg de sol. Après inoculation sur un support solide original, un développement fongique important a été observé dans le sol ainsi que la dégradation significative des polluants organiques (en moyenne 22% pour les HAP et 33% pour les polychlorobiphényles (PCB)) en moins de 4 mois
Soil contamination is a major issue today. In France, over 10,045 polluted sites and soils had been identified by mid-2022. According to a 2018 study, polycyclic aromatic hydrocarbons (PAHs) and trace metals (TMEs) were responsible for 14% and 23% of this pollution, respectively. Soil pollution has a significant impact on the biodiversity of ecosystems and human health. In the context of urbanisation policies and ‘zero net artificialisation’ of soils, the restoration of brownfield sites is of great interest, but the decontamination of soils co-contaminated with PAHs and TMEs remains a challenge. Mycoremediation, a process that uses the natural capacities of fungal strains to eliminate or transform certain pollutants present in an environmental matrix, is attracting growing interest due to the resistance of certain fungal strains to co-contamination and their ability to colonise soils through their mycelial network. This thesis work led to the development of new analytical tools for the semi-automated analysis of PAHs and certain oxygenated metabolites (ketones, quinones, hydroxylates) using thermodesorption coupled with tandem GC-MS/MS. A new method, using a cyclodextrin polymer, was applied to assess the bioaccessibility of PAHs in the industrial studied soil. A 6-month study in soil microcosms ruled out the use of the model strain Absidia cylindrospora for the mycoremediation of the studied soil: the high concentrations and availability of certain TMEs (Pb, Cu, Zn) and the very low bioaccessibility of PAHs meant that the fungal strain could not make a significant contribution to PAH biodegradation. Then new fungal strains were isolated from the industrial soil. An indigenous strain of Penicillium annulatum, resistant to Cu, Pb and Zn and capable of biodegrading PAHs, was selected for a larger-scale study, in a container that could hold 2 kg of soil. After inoculation thanks to an original solid support, significant fungal growth was observed in the soil, as well as significant degradation of organic pollutants (22% for PAHs and 33% for polychlorinated biphenyls (PCBs) on average) in less than 4 months

La fin des activités industrielles liées au charbon et à son exploitation a laissé de nombreux sites et sols pollués en France et particulièrement dans le Nord-est de la France. Une terre issue d'une friche industrielle de cokerie (Neuves-Maisons, Lorraine, France) est étudiée en couplant les outils de la science du sol et de la géochimie organique afin de comprendre l'évolution à long terme de la dynamique des contaminants. Une première étape de caractérisation de la terre et de sa pollution montre que la fraction limon fin (2-20 µm) est la fraction la plus réactive avec la plus forte concentration en HAP extractible et occlus et la plus faible disponibilité, mettant en évidence des processus de préservation spécifique au sein de cette fraction. Des extractions sélectives de la MO anthropique au solvant, confirmées par des observations au MEB, montrent que la MO anthropique, contrairement à la MO naturelle, n'a pas un rôle de liant entre les particules de la terre. L'apport de MO naturelle, (i) en conditions contrôlées par incubation de débris végétaux pendant 15 mois ou (ii) in situ en parcelles lysimétriques plantées avec de la luzerne pendant 6 ans, conduit à une structuration de la terre, une activité microbienne accrue et à l'incorporation et au stockage de la matière organique fraîche végétale dans les limons fins. En revanche, la pollution n'est pas affectée par l'apport de matière organique fraîche. Ainsi, la concentration et la disponibilité des HAP présentent une tendance à la diminution au cours du temps, que la terre soit cultivée ou non. Ainsi, la matière organique fraîche n'apparaît pas comme un agent de mobilisation de la pollution à long terme pour ce type de terre historiquement contaminée
The end of industrial activities associated to coal exploitation left many huge areas of wastelands especially in the Northeast of France. A former coking plant soil was studied with a combination of soil science and organic geochemistry tools in order to understand the evolution of the contaminants dynamic. In a first step, the soil and its pollution were characterized. The results showed that the fine silt fraction (2-20 µm) was the most reactive with the highest PAH concentration (extractable or occluded) and the lowest PAH availability. This fraction played a protective role toward the pollution. Moreover, solvent extractions of the anthropogenic organic matter showed that the anthropogenic organic matter was not a structuring agent between the particles in the soil. These observations were confirmed by SEM observations. In a vegetation growth context, (i) under controlled conditions with incubation of organic residue during 15 months and (ii) in situ in lysimetric plots planted with alfalfa during 6 years, the soil structure and the microbial biomass were promoted and the fresh organic matter was preferentially incorporated and stored in the fine silts. However, the pollution was not affected by the fresh organic matter addition. Both PAH concentration and availability showed a trend to decrease with the time of experiment. Thus, the fresh organic matter did not appear as a mobilizing agent for the pollution and would most probably contribute to pollution stabilization on the long term

Thesis (M.Sc. (Soil Science)) --University of Limpopo, 2013
The study was conducted to assess the impact of mining activities on selected soil physical, chemical and microbial properties on farmlands around three selected mining sites. Nine soil samples were collected from each of the following farms : Hans Merensky, Mogoboya and Leon Tom, Foskor Mine and JCI mining sites, respectively. Additional nine soil samples were collected from non-polluted Waterbok farm that serves as a control for the purpose of comparison. The samples were taken at 0–15, 15–30, 30–45 cm depths at three sampling points on each farm for physical, chemical and biological studies. However, soil samples collected for microbial (fungi, bacteria and actinomycetes) counts were surface (0–15 cm) soil samples. Soil chemical properties determined include pHw, electrical conductivity (ECe), exchangeable acidity (EA), organic carbon, available phosphorous, exchangeable cations as well as heavy metal (i.e. Mn, Zn, Cu, Pb, Cd, As and Sb) concentrations. The physical parameters determined include texture (sand, silt and clay) as well as bulk density. Soil pHw and ECe values decreased with depth; and ranged from 6.94 to 6.50 and from 12.24 to 10.76 mS cm-1, respectively. Exchangeable acidity showed a gradual increase with depth and ranged from 0.72 to 0.80 cmol(+)(kg), while percent organic carbon decreased with depth ranging from 1.41 to 2.19 %. Exchangeable cations, particularly K and Mg increased with depth while Ca decreased marginally with soil depth. Available phosphorous content decreased following increases in distance from the pollution source while heavy met.al contamination decreased with soil depth but increased further away from the pollution source. Significantly high loads of Pb, As and Sb were recorded at all depths on the three farms around the mining sites, which were largely responsible for the pollution but worse on the Leon Tom farm; with Pb constituting the greatest pollutant. The concentration of extractable heavy metals in the studied areas was in the order: As >Sb>Pb>Zn>Cu >Mn >Cd. Cadmium level appeared generally very low in all samples while elevated levels of Mn, Cu and Zn were detected at all depths in the polluted soils.Significant differences in microbial levels were detected at the various sampling points. The highest count of 3.82 and 6.20 CFU g-1 for fungi and actinomycete, respectively were both from the Leon Tom farm, while 6.46 CFU g-1 counts for bacteria was obtained from Mogoboya farm. Interestingly, fungal and actinomycetes activities were more sensitive to heavy metal contamination than bacteria that were significantly increased following soil pollution.
National Research Foundation (NRF)

Rural people around the 4 km2 Orathupalayam Dam in southern India live in one of India’s most polluted areas. The people were once restricted mainly by scarcity of water but today they cannot drink their well water or cultivate their soil. The dam, created to store floodwater from the Noyyal River, also stores effluent water from the more than 700 dyeing and bleaching industries situated in the town of Tiruppur, 20 km upstream. Although most industries have treatment plants they do not treat total dissolved solids (TDS) and thus NaCl becomes one of the major components of the effluent. 75 to 100 million litres of effluents are released every day.

Through water sampling in open and bore wells, and with the help of GPS, ArcView and Surfer it could be concluded that high TDS levels and concentrations of Cl-, Ca2+, Mg2+ and Na+ were associated with the dam. A definite spatial pattern of the spreading of polluted water could be determined. Water from the dam was fed to the ground water all around the dam and also affected the groundwater more than 4 km to the southeast. Soil samples and interviews with farmers made it clear that land irrigated with dam water or affected well water soon became uncultivable. The water destroyed the soil structure and seeds did not germinate after irrigation with polluted water.

Through interviews it could be concluded that the local people around the dam paid a large part of the externalities of the polluting activities of the textile industries in terms of negative health effects and lost agricultural land, water resources, fishing and working opportunities. These problems have mostly been caused by the high salt concentration in the effluents but it is unclear to what extent other substances have caused or might cause harmful effects to the environment, people and animals.

L'objectif était d'étudier la mobilité des HAP contenus dans un sol industriel pollué. Après une caractérisation physico-chimique du sol, les différentes expériences de lixiviations menées sur ce sol ont montré que la mobilité des polluants concernait à la fois les polluants sous forme dissoute et sous forme particulaire. Malgré une pollution massive du sol, le relargage des HAP sous forme dissoute est très limité en particulier pour des températures voisine de 15°C. Par contre le relargage devient significatif lorsque la fraction particulaire est prise en compte. Tandis que le relargage de la fraction dissoute est régulier dans le temps, le relargage particulaire n'est que temporaire : il apparaît lorsque la force ionique de la solution lixiviante est suffisamment faible et se termine quand le potentiel de HAP particulaires du sol est épuisé
The aim of this work was to study the mobility of PAH contained in a polluted industrial soil. After having established the physical and chemical features of the soil, the various lixiviation tests have revealed that both dissolved and particulate pollutants were concerned by the mobility of PAH. In spite of a heavy pollution of the soil, the release of dissolved PAH is limited particularly when the temperature during lixiviation is about 15°C. On the opposite, the release is quite significant when the particulate part is taken into account. The study revealed that the release of the dissolved part is regular, even with time whereas is temporary. It occurs when ionic strength of the leaching is low enough and it ends when there is no more particulate PAH in the soil

Une unité pilote de traitement thermique en continu de terres polluées par des composés organiques a été mise au point pour étudier la faisabilité du procédé de désorption thermique au niveau préindustriel. L'influence des principaux paramètres (température, pression, temps de séjour et débit d'air de balayage) est étudiée avec un sol initialement pollué à 1% en HAP et a permis de montrer que la température et le débit d'air de balayage sont les facteurs prépondérants pour obtenir une faible teneur résiduelle en HAP. Un essai réalisé en optimisant tous les paramètres a permis de dépolluer une terre polluée par des HAP avec une efficacité proche de 100%. Un bilan de matière effectué sur les principaux constituants du sol a permis de suivre leur cheminement dans l'unité pilote et de vérifier l'efficacité du traitement des terres et des effluents gazeux : le suivi du flux des HAP a montré que la teneur en COV dans les gaz rejetés à l'atmosphère était largement inférieure aux limites réglementaires. Des essais comparatifs réalisés avec des sols de nature différente et de teneurs en HAP voisines entre le traitement thermique en statique (autoclave) et en continu indiquent que ces deux procédés ont des impacts différents sur les taux de décontamination et que le traitement en statique ne peut donc pas servir d'outil préliminaire à l'étude du traitement thermique d'un sol pollué. Le transport des polluants organiques dans une particule de sol soumise à une élévation de température a également été modélisé. Une étude paramétrique dans le cadre de ce modèle a permis d'observer l'influence des différentes caractéristiques du grain de sol (porosité, surface spécifique, tortuosité et diamètre) et d'observer l'importance du transport par diffusion des polluants dans le grain de sol dans le phénomène de décontamination.

La prévision du comportement à court et moyen terme du mercure dans un sol de surface nécessite de déterminer, d’une part, les mécanismes prépondérants caractérisant sa migration potentielle et, d’autre part, l’évolution de ses formes chimiques dans cet environnement. Le site industriel étudié, localisé dans la plaine de la Crau (Sud Est de la France) a été pollué initialement avec du mercure sous forme métallique. Des extractions chimiques ont mis en évidence la présence de méthylmercure jusqu’à 1 mg/kg de sol, traduisant une transformation du mercure métallique. Elles ont aussi montré la présence de mercure potentiellement mobile dans la solution du sol, pouvant atteindre 16% du total selon les horizons, cette mobilité augmentant avec la profondeur. Par ailleurs, la mise au point de colonnes spécifiques a permis de démontrer la migration ascendante du mercure, en phase gazeuse, ainsi que sa refixation, forte, dans les horizons de surface. Au final, il a été montré l’existence d’une double circulation du mercure dans les sols du site : l’une ascendante, sous forme gazeuse, conduisant à une ségrégation poussée du mercure ; l’autre aqueuse et descendante où l’élément est potentiellement plus mobile
The forecast of the short and medium term’s behavior of mercury in a surface soil requires the determination, on the one hand, the main mechanisms characterizing its potential migration and, on the other hand, the evolution of its speciation, in this environment. The industrial site studied here, located in the plain of Crau (south of France), was initially polluted with metalic mercury. Chemical extractions highlighted the presence of methylmercury up to 1 mg/kg of soil, pointing out the transformation of metal mercury. They’ve also shown the presence of potential labile mercury in the soil solution, reaching 16% of the total depending of the layer, this mobility increasing with depth. Moreover, the development of specific columns made it possible to show an ascending mouvement of mercury, in the gas phase, and its strong re-fixation, in the surface layer. Finally, the existence of a double circulation of mercury inside the soil of this particular site has been shown : one ascending, in gas phase, leading to a tight segregation of mercury; the other, in aqueous phase and downward, where the element

Increasing soil degradation and its consequences on overall ecosystem services urge for restoration strategies. Construction of Technosols through assemblage of treated soil and industrial wastes is an innovative technology for the restoration of polluted land and re-use of industrial by-products. Recent studies have evidenced that Technosols could support ecosystemic services such as primary production but the knowledge about other soil functions, such as biogeochemical cycling, is limited. Due to the significant contribution of microbial communities to soil functioning, this PhD work was carried out to study the effect of the type of Technosol on microbial communities with a focus on functional guilds involved in N cycling. For this purpose, the abundance and diversity of the total bacterial community and the abundance of crenarchaeal community together with the abundance and activities of the nitrifying and denitrifying communities were investigated in two types of Technosols. Results demonstrated that diversity and composition of the bacterial community were similar to 'natural soils' and were not significantly different between the two Technosols with Proteobacteria being the dominant phylum (50-80%). The bacterial ammonia oxidizers were greater in number than crenarchaeal ammonia oxidizers but also correlated to the potential nitrification activity suggesting that bacteria are the dominant ammonia oxidizers in Technosols. The abundance of both the ammonia oxidizers and the denitrifiers were in the same range than that observed in other soil systems. Analyses of the vertical distribution of the activity and abundance of N-cycling communities in the Technosols showed a significant depth-effect, which was more important than the Technosol type-effect. Technosols physicochemical properties and the abundance of the bacterial ammonia oxidizers were the main drivers of the nitrification activity whereas the denitrification activity was controlled mainly by the Technosols physicochemical properties and, to a minor extent, by the abundances of the nirS denitrifiers. The estimation of the functional stability of the denitrification process against the heat-drought stresses revealed that Technosol exhibited the high resistance and resilience in comparison to the thermally treated soil. This work highlighted the potential of constructed Technosols to ensure the N cycling ecosystem services, along with a high capacity to resist and recover from environmental stresses, suggesting that construction of Technosols is a promising technology and a solution for the restoration of industrial wastelands and waste recycling

L'augmentation de la dégradation des sols et ses conséquences sur les services écosystémiques nécessite le développement de stratégies de restauration de ces sols. La constitution de Technosols, résultant de l’assemblage de sols pollués et de déchet industriels, est une approche innovatrice pouvant à la fois permettre de restaurer les sols et de recycler des sous-produits industriels. Des études récentes ont mis en évidence que les Technosols pouvaient assurer des services écosystémiques tels que la production primaire. Toutefois, notre connaissances des autres services écosystémiques rendus par les Technosols tels que les cycles biogéochimiques est limitée. En raison de la contribution significative des communautés microbiennes aux cycles biogéochimiques dans les sols, l’objectif de ce travail de thèse était l’effet du type de Technosol sur les communautés microbiennes et plus particulièrement les communautés fonctionnelles impliquées dans le cycle de l’azote. Dans ce contexte, (i) la densité et la diversité de la communauté bactérienne totale, (ii) la densité de la communauté crenarchéenne ainsi que (iii) la densité et les activités des communautés nitrifiante et dénitrifiante ont été étudiées dans deux types de Technosols différents. Les résultats obtenus montrent que la diversité et la composition de la communauté bactérienne des deux Technosols n'étaient pas significativement différentes entre elles, et similaires à celles de ‘sols naturels’, les Proteobacteria étant le phylum dominant (50-80%). La densité de la communauté bactérienne oxydant l’ammonium était non seulement plus importante que celle des crenarcheae qui oxyde l’ammonium, mais est également corrélée avec l'activité potentielle de nitrification suggérant ainsi que les bactéries sont responsables de l’oxydation de l’ammonium dans les Technosols. La densité des dénitrifiants et de la communauté oxydant l’ammonium sont du même ordre de grandeur que celles observées dans les sols agricoles. L’analyse de la distribution de l'activité et de la densité des communautés nitrifiante et dénitrifiante dans les différents horizons des Technosols montre un effet négatif de la profondeur, cet effet étant plus marqué que l’effet du type de Technosol étudié. Les propriétés physico-chimiques des Technosols et la densité de la communauté bactérienne oxydant l’ammonium sont corrélés à l'activité de nitrification alors que l'activité de dénitrification était contrôlée principalement par les propriétés physico-chimiques des Technosols, et dans une moindre mesure par la densité de la communauté dénitrifiant possédant le gène nirS. L'estimation de la stabilité fonctionnelle du processus de dénitrification vis-à-vis de périodes stress hydrique et thermique a montré que les Technosols présentaient une plus haute résistance et une meilleure résilience que des sols remédiés par traitement thermique uniquement. Ce travail souligne le potentiel des Technosols à assurer les services écosystémiques tels que le cycle de l’azote, ainsi que leur forte capacité à résister et à se remettre de stress environnementaux. Tout ceci semble donc indiquer que la construction de Technosols est une technologie prometteuse qui pourrait permettre la restauration de friches industrielles et le recyclage des déchets industriels
Increasing soil degradation and its consequences on overall ecosystem services urge for restoration strategies. Construction of Technosols through assemblage of treated soil and industrial wastes is an innovative technology for the restoration of polluted land and re-use of industrial by-products. Recent studies have evidenced that Technosols could support ecosystemic services such as primary production but the knowledge about other soil functions, such as biogeochemical cycling, is limited. Due to the significant contribution of microbial communities to soil functioning, this PhD work was carried out to study the effect of the type of Technosol on microbial communities with a focus on functional guilds involved in N cycling. For this purpose, the abundance and diversity of the total bacterial community and the abundance of crenarchaeal community together with the abundance and activities of the nitrifying and denitrifying communities were investigated in two types of Technosols. Results demonstrated that diversity and composition of the bacterial community were similar to ‘natural soils’ and were not significantly different between the two Technosols with Proteobacteria being the dominant phylum (50-80%). The bacterial ammonia oxidizers were greater in number than crenarchaeal ammonia oxidizers but also correlated to the potential nitrification activity suggesting that bacteria are the dominant ammonia oxidizers in Technosols. The abundance of both the ammonia oxidizers and the denitrifiers were in the same range than that observed in other soil systems. Analyses of the vertical distribution of the activity and abundance of N-cycling communities in the Technosols showed a significant depth-effect, which was more important than the Technosol type-effect. Technosols physicochemical properties and the abundance of the bacterial ammonia oxidizers were the main drivers of the nitrification activity whereas the denitrification activity was controlled mainly by the Technosols physicochemical properties and, to a minor extent, by the abundances of the nirS denitrifiers. The estimation of the functional stability of the denitrification process against the heat-drought stresses revealed that Technosol exhibited the high resistance and resilience in comparison to the thermally treated soil. This work highlighted the potential of constructed Technosols to ensure the N cycling ecosystem services, along with a high capacity to resist and recover from environmental stresses, suggesting that construction of Technosols is a promising technology and a solution for the restoration of industrial wastelands and waste recycling

Afin d'établir l'impact et le risque lié aux fertilisants chimiques depuis leur fabrication jusqu'à leur amendement sur la contamination des sols par les éléments traces métalliques, une étude de leur mobilité et leur transfert s'avère nécessaire. L'objectif de ce travail de thèse était d'évaluer la source de contamination du sol par les éléments traces autour de l'industrie des fertilisants chimiques et suivre l'évolution temporelle de la mobilité et du transfert de ces éléments dans un profil du sol agricole amendé par des engrais phosphatés du type simple superphosphate (SSP) ou du phosphogypse. Pour cela nous avons utilisé des techniques permettant la caractérisation structurale et minéralogique des sols collectés comme la diffraction des rayons X et la microscopie électronique. Puis une caractérisation chimique des sols collectés concernant la concentration totale des éléments traces et des éléments majeurs a été établie. Comme la mobilité n'est pas stable au cours du temps dépendant de plusieurs paramètres physico-chimiques comme le pH, le potentiel redox, la teneur en matière organique, une extraction séquentielle a été adoptée le long de l'étude au cours du temps et dans le profil du sol amendé jusqu'à une profondeur de 55 cm. En outre, l'absorption des éléments traces par les plantes cultivées sur le terrain agricole amendé par les engrais ou le phosphogypse a été analysée au cours du temps afin d'évaluer le risque lié à la chaîne alimentaire et plus particulièrement la chaîne alimentaire humaine induisant des effets négatifs sur la santé. Une comparaison entre l'application du phosphogypse et celle des engrais a été mise en évidence à la finalité de ce travail
To determine the impact and risk of chemical fertilizers, from their manufacture to their amendment, on soil contamination by trace metals, the study of their mobility and transfer would be necessary. The objective of this work was to evaluate the source of soil contamination by trace elements around the industry of chemical fertilizers, and to follow the temporal evolution of mobility and transfer of these elements in the profile of agricultural soil amended by superphosphate (SSP) fertilizers or phosphogypsum. To achieve our objective, we used techniques allowing the determination of structural and mineralogical characterization of collected soil samples, such as X-ray diffraction and electron microscopy. Chemical characterization related to the total concentration of trace and major elements of collected soils was established. As mobility was unstable over time, depending on several physico-chemical parameters such as pH, redox potential, and organic matter content, a sequential extraction was adopted throughout the study over time in the amended soil profile to a depth of 55 cm. In addition, the absorption of trace elements by agricultural crops cultivated over land amended with fertilizer or phosphogypsum was analyzed over time to assess the risk of their transfer to the food chain, especially the human food chain, imposing health hazards. A comparison between the effects of the application of phosphogypsum and phosphate fertilizer was carried out in concluding this work

Ce travail s'inscrit dans les grandes problématiques actuelles traitant des interactions environnement-santé en contexte minier. L'objectif est de décrire l'origine et l'impact sur l'environnement et la santé des pollutions liées aux activités d'extraction et de fonte polymétalliques (Ag, Au, Cd, Cu, Pb, Sb, Sn, Zn) dans la ville minière d'Oruro, en Bolivie. Des échantillons d'eaux de consommation et de surface, de sols, de poussières de sol, d'aérosols (PM2,5 et PM10) et de bioaccumulateurs de la contamination atmosphérique (Tillandsias capillaris) ont été caractérisés géochimiquement (ICP-MS) et minéralogiquement (DRX, MEB). L'ensemble des compartiments " eaux ", " sols " et " atmosphère " de la zone urbaine est contaminé en Eléments Trace Métalliques (ETM), notamment à proximité des mines et des fonderies (atteignant 16000 µ/g de Pb dans les sols ou 200 ng/m3 d'As dans les PM10 prés de la fonderie). Les différentes sources de contamination atmosphérique (érosion des terrils miniers, émissions des fonderies, transport de minerais) et leurs zones d'influence sont identifiées à l'aide d'études statistiques et d'interpolations spatiales. L'étude des sols et des poussières indique d'autres sources de contamination plus locales, comme une ancienne zone de stockage de minerais. Les séparations granulométriques des poussières montrent que les ETM sont globalement plus concentrés dans les fractions fines, mais pas nécessairement dans la fraction argileuse (< 2µm), généralement considérée comme étant la fraction la plus contaminée. La bioaccessibilité des poussières, mesurée par la méthode UBM, est globalement plus faible prés de la mine que de la fonderie, et varie en fonction de la fraction granulométrique et de l'élément considéré (jusqu'à 90% pour As et inférieure à 5% pour Sb et Sn). Le bilan d'exposition aux ETM des enfants selon leur quartier d'habitation (" centre ville ", " mine " et " fonderie ") est réalisé en prenant en compte l'ingestion et l'inhalation des poussières de sol et des aérosols. La prise en compte de la granulométrie et de la bioaccessibilité par fraction influe fortement sur les calculs de doses absorbées par l'organisme. Les doses absorbées calculées et les concentrations précédemment mesurées dans les cheveux des enfants sont corrélées. Dans cette étude, le Pb présente un comportement particulier : il présente des tenenurs très hautes dans les sols mais très faibles dans l'atmosphère. L'exposition est donc particulièrement liée au type et au lieu d'activité du sujet considéré et expliquerait la variabilité observée dans une étude épidémiologique antérieure
This work deals with current problematic issues of environment-health interactions. This thesis describes the origin of mining and smelting polymetallic pollution (Ag, Au, Cd, Cu, Pb, Sb, Sn, Zn) and its impact on environment and health in the mining city of Oruro, Bolivia. Samples of tap water, the hydrographic network, soils, dusts, aerosols (PM2,5 et PM10) and bioindicators of atmospheric contamination (Tillandsias capillaris) were geochemically (ICP-MS) and mineralogically (DRX, SEM) characterized. All the compartments of the urban area studied ("water ", "soil" and "atmosphere") were contaminated by trace elements, especially near smelters and mines (reaching 16000 µg/g Pb in dust and 200 ng/m3 As in PM10 close to the smelting area). Statistical studies and spatial interpolations helped in the identification of atmospheric contamination sources and their scope. Soil and dust studies also indicated other more local sources, such as old ore stockage areas. Granulometric separation of dusts showed that trace elements were more highly concentrated in fine fractions, but not necessarily in the clay (< 2µm), which is generally considered to be the most contaminated fraction. Oral bioaccessibility of dust fractions (UBM method), is higher overall in the smelting area than in the mining one. Bioaccessibility greatly varies depending on the granulometric fraction or elements considered (up to 90% for As and less than 5% for Sn and Sb). Exposure to trace elements in children depending on their place of residence was calculated considering dust and aerosol inhalation and ingestion. Taking into account granulometry and bioaccessibility can considerably change the absorbed dose calculated. Estimated exposure and trace element content in children's hair previously measured prove to be correlated. In this study, Pb showed a particular behaviour, with soil Pb concentrations were very high when compared to weak aerosol concentrations. Child exposure is thus greatly linked to type and location of the child's activities, which can explain the variability observed in a previous epidemiological study

Ce travail s'inscrit dans les grandes problématiques actuelles traitant des interactions environnement-santé en contexte minier. L'objectif est de décrire l'origine et l'impact sur l'environnement et la santé des pollutions liées aux activités d'extraction et de fonte polymétalliques (Ag, Au, Cd, Cu, Pb, Sb, Sn, Zn) dans la ville minière d'Oruro, en Bolivie. Des échantillons d'eaux de consommation et de surface, de sols, de poussières de sol, d'aérosols (PM2,5 et PM10) et de bioaccumulateurs de la contamination atmosphérique (Tillandsias capillaris) ont été caractérisés géochimiquement (ICP-MS) et minéralogiquement (DRX, MEB). L'ensemble des compartiments " eaux ", " sols " et " atmosphère " de la zone urbaine est contaminé en Eléments Trace Métalliques (ETM), notamment à proximité des mines et des fonderies (atteignant 16000 µ/g de Pb dans les sols ou 200 ng/m3 d'As dans les PM10 prés de la fonderie). Les différentes sources de contamination atmosphérique (érosion des terrils miniers, émissions des fonderies, transport de minerais) et leurs zones d'influence sont identifiées à l'aide d'études statistiques et d'interpolations spatiales. L'étude des sols et des poussières indique d'autres sources de contamination plus locales, comme une ancienne zone de stockage de minerais. Les séparations granulométriques des poussières montrent que les ETM sont globalement plus concentrés dans les fractions fines, mais pas nécessairement dans la fraction argileuse (< 2µm), généralement considérée comme étant la fraction la plus contaminée. La bioaccessibilité des poussières, mesurée par la méthode UBM, est globalement plus faible prés de la mine que de la fonderie, et varie en fonction de la fraction granulométrique et de l'élément considéré (jusqu'à 90% pour As et inférieure à 5% pour Sb et Sn). Le bilan d'exposition aux ETM des enfants selon leur quartier d'habitation (" centre ville ", " mine " et " fonderie ") est réalisé en prenant en compte l'ingestion et l'inhalation des poussières de sol et des aérosols. La prise en compte de la granulométrie et de la bioaccessibilité par fraction influe fortement sur les calculs de doses absorbées par l'organisme. Les doses absorbées calculées et les concentrations précédemment mesurées dans les cheveux des enfants sont corrélées. Dans cette étude, le Pb présente un comportement particulier : il présente des tenenurs très hautes dans les sols mais très faibles dans l'atmosphère. L'exposition est donc particulièrement liée au type et au lieu d'activité du sujet considéré et expliquerait la variabilité observée dans une étude épidémiologique antérieure.

Afin d'établir l'impact et le risque lié aux fertilisants chimiques depuis leur fabrication jusqu'à leur amendement sur la contamination des sols par les éléments traces métalliques, une étude de leur mobilité et leur transfert s'avère nécessaire. L'objectif de ce travail de thèse était d'évaluer la source de contamination du sol par les éléments traces autour de l'industrie des fertilisants chimiques et suivre l'évolution temporelle de la mobilité et du transfert de ces éléments dans un profil du sol agricole amendé par des engrais phosphatés du type simple superphosphate (SSP) ou du phosphogypse. Pour cela nous avons utilisé des techniques permettant la caractérisation structurale et minéralogique des sols collectés comme la diffraction des rayons X et la microscopie électronique. Puis une caractérisation chimique des sols collectés concernant la concentration totale des éléments traces et des éléments majeurs a été établie. Comme la mobilité n'est pas stable au cours du temps dépendant de plusieurs paramètres physico-chimiques comme le pH, le potentiel redox, la teneur en matière organique, une extraction séquentielle a été adoptée le long de l'étude au cours du temps et dans le profil du sol amendé jusqu'à une profondeur de 55 cm. En outre, l'absorption des éléments traces par les plantes cultivées sur le terrain agricole amendé par les engrais ou le phosphogypse a été analysée au cours du temps afin d'évaluer le risque lié à la chaîne alimentaire et plus particulièrement la chaîne alimentaire humaine induisant des effets négatifs sur la santé. Une comparaison entre l'application du phosphogypse et celle des engrais a été mise en évidence à la finalité de ce travail
To determine the impact and risk of chemical fertilizers, from their manufacture to their amendment, on soil contamination by trace metals, the study of their mobility and transfer would be necessary. The objective of this work was to evaluate the source of soil contamination by trace elements around the industry of chemical fertilizers, and to follow the temporal evolution of mobility and transfer of these elements in the profile of agricultural soil amended by superphosphate (SSP) fertilizers or phosphogypsum. To achieve our objective, we used techniques allowing the determination of structural and mineralogical characterization of collected soil samples, such as X-ray diffraction and electron microscopy. Chemical characterization related to the total concentration of trace and major elements of collected soils was established. As mobility was unstable over time, depending on several physico-chemical parameters such as pH, redox potential, and organic matter content, a sequential extraction was adopted throughout the study over time in the amended soil profile to a depth of 55 cm. In addition, the absorption of trace elements by agricultural crops cultivated over land amended with fertilizer or phosphogypsum was analyzed over time to assess the risk of their transfer to the food chain, especially the human food chain, imposing health hazards. A comparison between the effects of the application of phosphogypsum and phosphate fertilizer was carried out in concluding this work

El sòl és un recurs no renovable a curt i mitjà termini ja que els processos que generen un sòl són extremadament lents i requereixen de milers d’anys. A més a més, no és un sistema aïllat, sinó que presenta interaccions dinàmiques amb la geosfera, l’atmosfera i la hidrosfera, per la qual cosa està exposat a l’entrada de contaminants a través de moltes fonts de contaminació. L’origen dels metalls pesants en els sòls, que pot ser geogènic i antropogènic, marca el nivell de concentració, la forma química i la mobilitat a la qual es troben. La contaminació per metalls pesants en sòls presenta un problema a causa de la seva persistència en el medi, ja que no es degraden. Per tant, la seva presència en sòls s’ha anat incrementant des dels inicis de la revolució industrial. Els metalls pesants més comuns en el sòl són el Pb, Zn, Cd i Cu, i l’As com a metal•loide, i la forma química en la que es troben influencia la seva solubilitat, mobilitat i toxicitat en els compartiments ambientals i a la cadena tròfica. La consideració d’un sòl com a contaminat comporta desenvolupar i aplicar actuacions de recuperació ambiental de l’emplaçament. En nombrosos casos, les intervencions per tractar la contaminació de sòls per metalls pesants es basen en l’addició de materials, el que permet augmentar la retenció dels contaminants i diluir la concentració dels mateixos en les mescles sòl+material resultants, amb la finalitat de fer menys accessible el metall pesant a les plantes i evitar la possible contaminació a altres compartiments ambientals i a la cadena tròfica. En base a aquesta problemàtica, la present tesi s’ha estructurat de la següent manera: Primerament, es va fer una comparació de mètodes analítics, prèvia validació, per a la determinació del contingut total d’elements en mostres inorgàniques d’interès ambiental entre diferents tècniques d’anàlisi directa (FRX i µFRX), i mètodes basats en una digestió humida (Aigua Règia i microones) seguida d’una quantificació amb ICP­OES i ICP-MS (detallat en la secció 2.1). Sent la digestió amb microones, combinada amb la mesura per una tècnica òptica adient, el millor mètode per a la determinació, tant d’elements majoritaris com traces, en matrius ambientals inorgàniques. També es van avaluar els tests de lixiviació per a predir la mobilitat de metalls pesants en mostres ambientals emprant tests basats en extraccions simples fent servir diferents agents extractants, tals com 0,01 M i 1M CaCl2, 0,43 M CH3COOH i 0,05 M EDTA i el test de lixiviació Influència del pH sobre la lixiviació amb addició inicial d’àcid/base (pHstat) (detallat en la secció 2.2). Tot i que la fracció extraïble dels metalls amb EDTA va ser major que la obtinguda en el punt de pHstat equivalent, comparant aquest valor amb el punt de pH més àcid del pHstat, es va observar que aquest últim era el que donava la lixiviació màxima dels metalls i per tant, permet estimar la fracció mòbil màxima de metall a llarg termini. Finalment es va establir una metodologia de laboratori per a la selecció de materials per la immobilització de metalls pesants en sòls contaminats (detallat en la secció 2.3). Sent els materials amb una elevada capacitat de neutralització àcida i/o capacitat de sorció específica els més prometedors els més adients en ésser addicionats per a la remediació de sòls contaminats amb metalls pesants. Aquesta metodologia es va aplicar per avaluar l’eficiència de l’addició dels materials en un estudi a escala de planta pilot (detallat en la secció 2.4), on es van corroborar els resultats obtinguts prèviament a escala de laboratori.
Metal pollution in soils requires intervention actions to attenuate its impact. In-situ remediation of contaminated soils is recently receiving increasing attention since it is a more feasible and economically affordable approach than ex-situ strategies, especially when facing a large amount of soil to be remediated. In this context, the addition of materials, including non-hazardous wastes to contaminated soils may be a suitable remediation strategy due to a double mechanism: decrease in pollutant mobility and dilution of pollutant concentration (if large material doses are used). Candidate materials must ensure an increase in the pollutant-soil interaction by increasing the pollutant sorption in the resulting mixture and/or by modifying soil properties governing the leaching and related transport of the pollutants into groundwaters and trophic chain. Moreover, another indirect benefit from this remediation strategy is that it may allow the reuse of non-hazardous wastes generated by industrial processes. In order to give response on this lack of research, the thesis has been divided in the following parts: Firstly, it has done a comparison of analytical methods, previously validated, to determine the total content of elements in inorganic samples of methods that directly analyze samples without digestion (XRF and µXRF) and methods based on a previous wet digestion (Aqua Regia and Microwaves) followed by quantification with ICP-OES and ICP-MS (detailed in section 2.1). The microwave digestion was the best method to determine the total content of major and trace elements in inorganic environmental matrices. Also, it has done an evaluation of lixiviation tests to predict the mobility of heavy metals in environmental samples using simple extraction, 0,01 M and 1M CaCl2, 0,43 M CH3COOH and 0,05 M EDTA and the lixiviation test Influence of pH on leaching with initial acid/base addition (pHstat) (detailed in section 2.2). The EDTA extraction yield of metals was higher than pHstat, at the same pH, but if we compare with the most acidic pH of pHstat, we observed that the metal lixiviation was maxim, so the pHstat can estimate the maximum mobile fraction of the metal in a long period. Finally, it has done the establishment of the laboratory methodology to select the materials to immobilize the heavy metals in contaminated soils (detailed in section 2.3). The best candidates were those with a high acid neutralization capacity and/or specific sorption capacity. This methodology was applied in order to evaluate the efficiency of the materials in a pilot plant study (detailed in section 2.4). The results obtained in a pilot plant corroborated the results obtained in a laboratory scale.

L'oxydation de la pyrite par l'air conduit à la formation d'acide sulfurique qui est responsable de la lixivitation acide des sols et friches industrielles avec libération de métaux lourds. La limitation de cette oxydation, et la compréhension des mécanismes d'adsorption/désorption de l'argent et du mercure sur FeS[indice 2] sont parmi les objectifs de travail. L'adaptation de la Scanning Reference Electrode Technique (SRET), qui est une imagerie électrochimique habituellement utilisée pour la visualisation de phénomènes de corrosion localisée sur des comosés métalliques, a permis de mettre en évidence des sites anodiques et cathodiques lors de l'oxydation de la pyrite par l'oxygène atmosphérique. Elle a montré aussi que l'inhibition de cette réaction par le thymol passe par l'oxydation préalable de ce dernier à la sruface de minéral. Les conditions de fixation des ions Ag+ sur la pyrite sous forme de Ag[indice 2]S et de Ag° ont été précisées. Un composé de type Fe[indice t-x]Ag[indice 2x]S[indice 2] a été mis en évidence en milieu dilué. La SRET a montré que la fixation de l'argent sur la pyrite est rapide et passe par une processus galvanique. Contrairement à ce qui se passe avec l'argent, la fixation des ions Hg[exposant 2+] sur le minéral passe par des réactions de surface et conduit à la formation de deux espèces du mercure de stabilités différentes qui peuvent être mises en évidence par voltampérométrie. Là aussi un processus reodx ne peut pas être exclu. Pour l'espèce la plus stable, un complexe de surface =S-S-Hg-OH est proposé. L'espèce la moins stable pourrait correspondre à "SO[indice 3], 3HgO". Tandis que la présence d'ions Hg[exposant 2+] en solution interdit la fixation de Ag[exposant +] sur la pyrite et désorbe l'argent fixé lors d'un conditionnement préalable du minéral avec Ag [exposant+], elle ne modifie pratiquement pas l'adsorption des ions Cu[exposant 2+] et ne désorbe pas le cuivre initialement présent sur le minéral.

Ce travail traite d'une partie souvent oubliée de la ville, le sous-sol peu profond qui accueille les réseaux, les racines de la végétation, les déchets urbains, à travers le cas français, parisien en particulier. Dans une première partie, on met en exergue les dysfonctionnements actuels de la pédosphère urbaine : dégradations des réseaux, de la végétation, perturbation des nappes, etc. Dans la seconde partie, on recherche les racines historiques de la perte de connaissance sur le sol urbain en analysant les doctrines scientifiques et techniques qui se succèdent du XVIIIe au XXe siècles chez les médecins, géographes et ingénieurs. On montre comment les premiers ont analysé le rôle du sol dans l'épidémiologie urbaine au XVIIIe siècle puis ont perdu cette sensibilité dès la restauration en substituant la statistique à l'observation, avant de se tourner vers le milieu intérieur à la fin du XIXe siècle. Les géographes ont permis, malgré de nombreuses difficultés, la reconnaissance de la topographie urbaine en élaborant les outils cartographiques de représentation du relief, qui sont repris par les ingénieurs des Ponts et Chaussées auxquels est confiée au XIXe siècle la rectification de la ville. On insiste sur les difficultés que rencontrent ces derniers à saisir la nature du sol, qui se traduit par la mathématisation de la poussée des terres et l'empirisme dans les techniques de fondation. Les transformations de la ville, ébauchées sous le Premier Empire, entraînent dès la Monarchie de Juillet une série de dysfonctionnements dans la gestion du sol urbain : revêtement des rues, apparition du déchet liquide. Le sol industriel n'est plus considéré pour sa valeur artisanale ou son rôle délétère mais accueille parfois les eaux usées et est ravalé au rang de filtre. Si l'automobilisme permet l'accomplissement de la ville abiotique, on souligne le désintérêt des urbanistes, des hygiénistes (rarement médecins), des mécaniciens des sols du premier XXe siècle pour le milieu urbain. Un regain d'intérêt pour le sol urbain se manifeste dans l'Entre-deux-guerres, mais dans une nouvelle perspective, celle de l'urbanisme souterrain. Ces deux siècles et demi conduisent au chaos actuel du sous-sol et traduisent non seulement la complexité de l'industrialisation du sol mais aussi le désintérêt progressif de certaines disciplines scientifiques pour la ville dans laquelle elles ont vu le jour.

En France et en Europe, la fin des activités industrielles liées à l’exploitation du charbon a laissé de nombreux sites et sols pollués par les hydrocarbures aromatiques polycycliques (HAP). La rhizodégradation pourrait permettre leur dépollution par l’utilisation de plantes et de leur microflore associée. Toutefois, l’efficacité de cette technique, démontrée en conditions contrôlées de laboratoire, est limitée in situ par de fortes mortalités ou l’inhibition de croissance de la plante. De plus, le transfert de ces polluants dans la plante peut menacer la chaîne alimentaire. Ce travail se propose d’étudier les interactions entre le maïs, choisi ici comme plante modèle, et les HAP de sols industriels contaminés ou un de leur représentant, le phénanthrène ajouté à un substrat simplifié. Le prélèvement des HAP et leur effet sur la physiologie de la plante sont évalués sur des systèmes de complexité croissante et en abordant ces questions à différentes échelles, allant de la cellule à la plante entière. Il s’agit en particulier d’élucider les mécanismes de transfert et de translocation des HAP dans la plante et d’identifier les réponses toxiques de celle-ci. Les résultats mènent à l’hypothèse d’une sorption physique des HAP de la phase solide du sol par contact direct avec les racines comme mécanisme principal d’entrée et non par transport dans la phase aqueuse. Les principaux arguments sont les distributions moléculaires similaires entre les HAP totaux dans les terres et celles dans les racines, les mauvaises corrélations entre les concentrations en HAP dissous dans l’eau porale et les racines, ainsi que la surestimation des concentrations prédites par des modèles existants fondés sur un prélèvement de la solution du sol. La localisation du PHE dans les racines à l’aide d’outils de microscopie montre une subérification précoce de l’exoderme et l’endoderme, même à de faibles teneurs (50 mg kg-1). Le prélèvement de nutriment ne semble pas affecté mais d’importantes accumulations et carences d’éléments sont observées dans les parties aériennes. Ces perturbations nutritionnelles du maïs pourraient affecter le fonctionnement de la plante et par conséquent limiter sa croissance ou entraîner sa mort
In Europe and France, the end of industrial activities associated to coal exploitation left numerous wastelands contaminated with polycyclic aromatic hydrocarbons (PAH). Rhizodegradation enables their remediation by using plants associated with microflora. However, the efficiency of this technique, demonstrated at the laboratory scale, is often limited in situ by high plant mortality or inhibited growth. Furthermore, the PAH uptake in plants may threaten the food chain. This work studied the interactions between maize, chosen as model plant, and PAH from industrial contaminated soils or from simplified model systems, i.e. sand spiked with phenanthrene. PAH uptake and their effect on the plant physiology were assessed using systems of increasing complexity, to solve questions raised at different scales, from the cell to the whole plant. Mechanisms involved in PAH uptake and translocation are proposed and the toxic responses of the plant are detailed. Results lead to a new hypothesis: PAH from the solid phase penetrate the roots by physical and direct contact and not only through uptake in pore water. Main arguments are: similar molecular distributions in soils and roots, low correlations between PAH concentrations in pore water and roots and overprediction of bioaccumulation by using predicting models based on root absorption in soil solution. Localization of PHE in roots using microscopic tools showed early suberisation of endoderm and exoderm in presence of PHE, even at low concentration (50 mg kg-1). Nutrient uptake seemed not affected but large elements accumulations and depletion were observed in aerial part of maize. These nutritional disruptions may affect plant functioning and consequently, decrease its growth or even cause its death

En zone urbaine ou industrialisée, la qualité des sols est particulièrement impactée par les émissions chroniques de contaminants. Pourtant, ces écosystèmes fragiles et fondamentaux sont non renouvelables à échelle de vie humaine, et leur préservation est essentielle pour répondre aux enjeux sanitaires et environnementaux actuels. Ce travail apporte de nouveaux éléments de connaissance sur la contamination métallique de sols urbain soumis à des retombées de poussières industrielles. Il s'intéresse particulièrement à la ville de Gravelines, située en bordure nord-ouest de l'agglomération dunkerquoise (Nord, France), à proximité de plusieurs industries métallurgiques et sidérurgiques. La signature chimique et morphologique de retombées de poussières (collectées au coeur de la ville) montre que dans certaines conditions météorologiques (vents de nord-est), la proportion de particules issues de sources industrielles est supérieure à 80% (particules riches en carbone, poussières d'alumine, laitiers, oxydes de fer...). Des enrichissements significatifs en métaux, détectés dans les retombées, permettent d'identifier les éléments Cr, Ni, Mo comme principaux traceurs des activités métallurgiques. La recherche de ces métaux traceurs dans les sols conduit à une évaluation de la vulnérabilité spatiale des sols de Gravelines aux retombées de poussières. Alors que l'hypothèse d'une pollution métallique généralisée est écartée, des niveaux de contamination notables en éléments traceurs métalliques sont identifiés à proximité des industries émettrices (ceinture de végétation, jardins ouvriers et cimetière au nord-est de la ville). Les profils de concentrations établis sur ces zones traduisent, en effet, un apport atmosphérique de contaminants, notamment dans les 3 premiers centimètres du sol. L'intégration des poussières dans les matrices pédologiques est, par ailleurs, confirmée par observation en microscopie électronique d'une lame mince de sol contaminé. Sous forme mobile dans les sols, les métaux traceurs des activités industrielles peuvent être toxiques pour les organismes vivants. L'étude de leur mobilité générale dans les sols de Gravelines révèle une relative stabilité de Cr, Ni et Mo, indiquant leur faible biodisponibilité lorsqu'ils sont issus de sources industrielles. Les sols étudiés présentent des niveaux d'écotoxicité intermédiaires. Ces derniers peuvent toutefois être ponctuellement plus élevés dans les zones les plus impactées par les dépôts industriels. Bien que le degré d'écotoxicité ne puisse être directement relié aux métaux apportés par les poussières industrielles, ce travail souligne tout particulièrement la question de l'usage des sols exposés à de tels dépôts
In urban or industrialized areas, soil quality is particularly affected by chronic emissions of contaminants. Yet these fragile and fundamental ecosystems are non-renewable on a human timescale, and their preservation is essential to respond the current health and environmental challenges. This work provides new knowledge on metallic contamination of urban soils submitted to industrial dust deposition. It focuses, in particular, on the town of Gravelines, located in the Dunkerque agglomeration (Northern France) close to several metallurgical and steel industries. The chemical and morphological signature of dust fallout (collected in the city center) shows more than 80% of particles coming from industrial sources (carbon-rich particles, alumina dust, slag, iron oxides, etc.) in certain weather conditions (northeast winds). Significant metal enrichment detected in the dust fallout allows to identify the elements Cr, Ni and Mo as the main tracers of metallurgical activities. Concentrations of tracer metals in soils enables an assessment of the spatial vulnerability of Gravelines soils to dust fallout. While the hypothesis of generalized metallic pollution has been ruled out, significant levels of contamination in tracer elements were identified in the vicinity of emitting industries (in the northeast areas of the town). Concentration profiles in these areas suggest an atmospheric input of contaminants, with higher metal enrichment in the soil subsurface. The integration of dust into soil matrices is partially confirmed by electronic microscopic observations of a thin section of contaminated soil. When mobile in soils, trace metals from industrial activites can be toxic to living organisms. A study of their general mobility in Gravelines soils reveals the relative stability of Cr, Ni and Mo, indicating their low bioavailability when derived from industrial sources. Globally, the studied soils show intermediate levels of ecotoxicity. However, the latter one is punctually higher in areas most affected by industrial deposits. Although this toxicity was not directly related to the industrial dust-borne metals, this work is particularly highlights the question of the use of soils exposed to such deposits

L'industrie sucriere, basee sur la betterave a sucre, donne une quantite importante de pulpe, un dechet dont il n'a pas encore ete trouve d'utilisation en tant que source de materiaux. Cette pulpe de betterave est compose essentiellement de polysaccharides et est particulierement riche en fonctions hydroxyles. Alors que l'oxypropylation de la cellulose, de la lignine et plus recemment du chitosane, aient ete etudiees, aucune investigation equivalente sur la pulpe de betterave n'a ete conduite avant ce travail. Le but de cette etude a ete de transformer un solide insoluble dans tous les solvants en un polyol liquide visqueux adapte a l'elaboration de polyurethanes apres melange avec des polyisocyanates. La premiere etape de ce travail consistait a examiner la faisabilite puis a optimiser la reaction d'oxypropylation de la pulpe de betterave a sucre. La reaction a ete menee en suspendant la pulpe dans de l'oxyde de propylene (op) en presence de differents catalyseurs basiques et en chauffant ce melange sous pression. En faisant varier differents parametres, on obtient des polyols possedants des viscosites et des indice d'oh differents. Il s'avere que ces liquides visqueux sont en fait des melanges homogenes de pulpe oxypropylee et d'homopolymeres de op. Ces polyols ont ete utilises seuls ou en combinaison avec des extenseurs de chaines (diols d'origines diverses) pour l'elaboration de polyurethanes a la fois sous forme de materiaux pleins (en utilisant le procede rim) et de mousses. Les cinetiques de ces polymerisations ainsi que la caracterisation des materiaux obtenus ont ete correlees avec la composition du melange reactionnel. Les proprietes de ces nouveaux polyurethanes suggerent que la pulpe de betterave a sucre peut constituer un dechet agroindustriel viable, base sur l'exploitation agricole d'une ressource renouvelable, pour l'elaboration de materiaux polymeres originaux.

The industrial port of Richards Bay on the eastern seaboard of KwaZulu-Natal, South Africa has undergone rapid growth over the last 25 years. This industrial growth has inevitably led to an increase in the anthropogenic pollutant inputs in the area. However, the degree of this contamination has not previously been assessed not been accompanied by an awareness of its environmental impacts. This project serves to assess the current environmental situation of the area and provide background levels against which the environmental impacts of further growth in the area can be assessed. The main pollution point sources in the area were identified as a pulp and paper plant, a sulfuric acid/fertiliser plant and aluminium smelters. The chemical and physical processes involved within these industries were identified and discussed in detail. The common inorganic pollutants emitted by these industries were identifies as trace metals, sulfur dioxide, NOx gases and fluoride. It was these pollutants that therefore became the focus of this study. Reservoirs within Richards Bay that may become sinks for contamination were identified and water, sediment and soil samples were taken from these reservoirs. The samples were analysed for trace metal contamination, pH, alkalinity and fluoride levels. Analysis of the acidity and alkalinity of water, sediment and soils samples demonstrated that there is presently no long-term acidification of the environment in Richards Bay. The only samples that showed increased acidity were the soils taken from the roadside sites immediately outside the industries. This lack of overall acidification indicates that, at present, there are no detrimental effects of acidic emissions on the hydrosphere and geosphere. Only cursory investigations were conducted into the fluoride levels found in water samples. None of the samples analysed demonstrated detectable amounts of fluoride present. Comprehensive trace metal analyses were performed on the water, sediment and soil samples through the use of ICP-AES. Levels obtained were compared with levels from samples taken from relatively uncontaminated background sites. Trace metal analysis indicated contamination of the freshwater reservoirs when compared with the background, while the soils and saltwater reservoirs remain largely uncontaminated. However, the contaminated areas did not show levels greater than quality guideline concentrations. Further studies should be conducted with regards to the trace metal contamination of the biosphere and the bioavailability of the contaminants already present in the waters, sediments and soils. More detailed investigations should also be conducted into the levels of atmospheric pollutants and fluoride levels in all reservoirs.
Thesis (M.Sc.) - University of KwaZulu-Natal, Pietermaritzburg, 2004.

Mining industry has been identified as the main sustenance of the South African economy, however the negative impacts of the industry on the ecological systems cannot be over emphasized due to the released waste which is mostly heavy metals into the environment. The study evaluated six heavy metal (A1, Cu, Fe, Ni, Pb and Cr) contents in a tailings dam from a specific mine site. Two sets of samples for the investigation were measured, that is, one in year 2012 and the other in year 2013. In the year 2012, the sample set was only taken at a distance profile of 500 meters from the foot of the dam, whereas the sample set taken in the year 2013 was for the 500 and 1500 meter distance profiles from the foot of the dam. The year 2012 and 2013 sample sets for the 500m distance profile were sampled very similarly to each other. A kilogram of each sample was taken as per grid format. The samples at varied depths were taken at 0-cm depth for the top layer, 20cm depth for the second layer, and 30cm depth for the third layer. The samples for the surface varied distance were taken at 1 m, 2m, 3m, and 4m away from each 500m and 1500 sampling points. The 2012 samples were analysed using characterization methods namely ICP MS and The 2013 samples were analysed using the ICP OES. The comparison of the field results for the six heavy metals studied (A1, Fe, Pb, Cu, Ni and Cr) was performed using statistical analytical methods, namely ANOVA. The statistical analysis results for heavy metals (A1, Fe, Pb, Cu, Ni and Cr) from sample and 2013 revealed that the group means are not significantly different from each other which means that there is no significant difference in (A1, Fe, Pb, Cu, Ni and Cr) concentrations with respect to both depth and distance. The observations from both 2012 and 2013 indicate the results of the samples are in agreement. In addition, the comparative average concentrations of the three results obtained reach the same conclusion that the tailing dam probably does not introduce considerable or significant amounts of these metals (A1, Fe, Pb, Cu, Ni and Cr) into the surrounding soils.
Chemical Engineering
M. Tech. (Chemical Engineering)

Dissertação de Mestrado em Geociências, Ambiente e Ordenamento, apresentada à Faculdade de Ciências e Tecnologia da Universidade de Coimbra.
Na área de estudo, localizada na zona peri-urbana de Coimbra (Zona Industrial da Pedrulha), esteve implantada a antiga fábrica “Fundições Gomes Porto, Lda”, já demolida e em cuja área, com 4 ha, ainda se encontram dispersos os resíduos resultantes da actividade dessa fábrica que laborou durante 40 anos, entre 1949 e 1990. Na área de estudo predominam as litologias margo-calcários, pertencentes à Orla Mesocenozóica, numa área que apresenta alguma fracturação. A mineralogia, os parâmetros fisíco-químicos e a química do solo da área da fábrica, mas também do solo regional foram estudadas, para compreender o impacte que a fábrica teve no solo. O solo apresenta valores de pH alcalinos, não havendo distinção significativa entre o pH do solo regional e o pH do solo da área da fábrica. Não há diferença significativa entre a condutividade elétrica entre o solo regional e o solo da área da fábrica, sendo que este último apresenta um intervalo de variação superior. O solo regional apresenta teores de matéria orgânica e de humidade superiores ao solo da área da fábrica. O solo da área da fundição mostra ter características texturais e mineralógicas distintas do solo regional, com textura arenosa e constituído maioritariamente por quartzo. O solo regional tem textura franco a franco-siltosa e é constituído maioritariamente por calcite. Os minerais de argila mais abundantes presentes no solo foram caulinite e ilite, não apresentando distinção significativa entre os dois solos analisados quanto ao tipo e quantidade de argilas. O solo da área da fábrica apresenta maiores teores de SiO2, TiO2, Al2O3, Fe2O3, Zr, Sr, Rb, Pb, Zn, Cu, V, Nb e Bi do que o solo regional. Os resíduos de fundição apresentam elevadas concentrações de Zr, Zn, Cr, Cu, Ni, Sn, As e Pb que justificam os maiores teores destes elementos no solo da área da fábrica em relação ao solo regional. O solo da área da fábrica encontra-se poluído em Cu e Pb cuja média dos valores dos teores é 138 mg/kg e 131 mg/kg, respectivamente e em alguns locais em As, Cr e V, e está contaminado em Al2O3 (7,71%), Fe2O3 (4,56%), SiO2 (36,59%), Th (19mg/kg), V (73 mg/kg), Zn (291 mg/kg), Rb (91 mg/kg), Zr(737 mg/kg) e Bi (17mg/kg), tendo em conta a legislação Canadiana de solos e o fundo geoquímico Português e Europeu. Não existe uniformidade na disposição dos contaminantes e poluentes na área de estudo, havendo uma relação com os locais de armazenamento, vazamento e acabamento das peças e do tipo de matéria prima utilizada. A indústria de fundição é um sector essencial para o desenvolvimento da economia nacional, sendo fornecedora de diversos tipos de indústrias, dos mais diversos sectores. Contudo, sem a devida gestão de resíduos, esta indústria poderá ter impactes negativos significativos no ambiente, como foi o caso do impacte que os resíduos da antiga Fábrica de Fundição Gomes Porto teve nos solos onde esteve implantada.
The studied area is located in the surrounding area of Coimbra (Pedrulha Industrial Park), where between 1949 and 1990, operated the foundry Fundições Gomes Porto, Lda. The foundry was already demolished but in its 4 Ha terrain we could find dispersed residues, as the result of the 40 years of the foundry’s activity. This area is today dominated by margo-limestone lithologies belonging to the Mesocenozoic Edge in an area that shows some fracturing. The mineralogy, physicochemical parameters and soil chemistry of the foundry’s area, were studied and compared with regional soil parameters to understand the impact that the foundry had on the soil. The soil presents alkaline pH values, with no significant differences between the regional soil pH and soil pH of the foundry area. There is no significant difference between the electrical conductivity between the regional soil and the foundry soil, although this has a greater variation range. The regional soil presents higher values of organic material and moisture than the foundry’s area. The foundry soil has different textural and mineralogical characteristics when compared with the regional soil. The foundry’s soil has a sandy texture and consists mainly of quartz, where the regional soil has a frank to frank-silty texture and consists mainly of calcite. The most abundant clay minerals in the soil were kaolinite and illite, with no significant difference between the regional soil and the foundry soil as the type and amount of clay. The foundry soil has higher contents of SiO2, TiO2, Al2O3, Fe2O3, Zr, Sr, Rb, Pb, Zn, Cu, V, Nb and Bi than the regional soil. The foundry waste has high concentrations of Zr, Zn, Cr, Cu, Ni, Sn, As and Pb, which justify the higher levels of these elements in the foundry soil when compared with the regional soil. The soil in the foundry area is polluted factory in Cu and Pb with average values of the levels are 138 mg / kg and 131 mg / kg, respectively, and in some places in As, Cr, and V, and is contaminated in Al2O3 (7 , 71%), Fe2O3 (4.56%), SiO2 (36.59%), Th (19mg / kg), V (73 mg / kg) Zn (291 mg / kg), Rb (91 mg / kg ), Zr (737 mg / kg) and Bi (17mg / kg), given the Canadian legislation and the Portuguese and European soil geochemical ground. There is no uniformity in the disposition of contaminants and pollutants in the foundry’s area but there is a relationship of contaminants and pollutants in places of local storage, disposal and finishing with the type of material used. The foundry industry is a key sector for the development of the national economy as a supplier of many industries in different sectors. However, without proper waste management, this industry can have significant negative impacts on the environment, as shown in the study of the soil where the old foundry industry Fundições Gomes Porto operated.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand in fulfilment of the requirements for the degree of Master of Science Johannesburg 2017.
The development of the economy of South Africa and many other countries has been highly dependent on mining industries. Minerals such as gold, platinum, diamond and many others have been mined and continue to be mined. Despite the importance of these minerals, their processing comes with social and environmental problems. During the processing of these minerals, trace elements such as copper, chromium, nickel, mercury, uranium, molybdenum and many others are released as wastes into the environment either, directly or indirectly. The release of the elements into the soil is of concern due to the possibility of groundwater system contamination. The presence of these elements in the groundwater system poses serious challenges to the wellbeing of life forms, due to their toxicity, when they exceed threshold limits. From the processing plants, these elements could be released onto the soil, and mobilise to groundwater, increasing the already existing environmental crisis due to water pollution. Once these elements are in the water, access to living organisms becomes easier through the food chain. Some of these elements are not biodegradable and thus persist in the environment as well as in the bodies of living organisms. They can cause serious health problems because of their toxicity effect. In humans, these elements can be carcinogenic, and also cause chronic disorders, kidney failures, defects in infants, bone and vascular diseases which could also be lethal. It is therefore of importance that these elements are neither bioavailable nor bioaccessible to living organisms. When these elements are mobile in the soil, the probability of reaching groundwater increases. Water, an important natural resource should always be protected from such pollutants. The demand for unpolluted water has been rising every year in the world due to increasing population, extended droughts and improper disposal. This research was dedicated to determining the behaviour of elements in an agricultural soil impacted by mining activities. Agricultural soils are sometimes exposed to pollutants that could originate from dust fallout or precipitation; fertilisers and manure; pesticides; and water used for irrigation. Understanding the iv processes that control the distribution of these pollutants in agricultural soils is an important risk assessment measure, considering that such pollutants have the potential of being taken up by crops and vegetables or transported to groundwater. In this study, a soil on a farm that grows vegetables for commercial purpose. Cabbage, spinach, carrots and potatoes are some of the vegetables grown on the plot and sold to markets in Pretoria and Johannesburg. The plot is in the vicinity of smelting operations in the North West Province. The mobility of trace elements in the soil can be controlled, depending on the type and properties of soil. Hence in this research, the ability of the soil to adsorb elements entering the soil is studied. The batch experimental work was performed to determine the effect of pH, initial concentration (5 - 100 mg/L), competing ions (Fe3+, Ca2+, Co2+, Mg2+, K+, Ni2+ and Zn2+), fertilisers (ammonium nitrate, ammonium phosphate and calcium chloride) and plant exudates (acetic acid, citric acid and oxalic acid as well as ethylenediaminetetraacetic acid (EDTA) which is often used as proxy organic ligand (found in manure)) on the adsorption of cadmium (Cd), copper (Cu) and chromium (Cr) onto an agricultural soil. The PHREEQC geochemical modelling code was used to complement experimental methods in predicting processes and to further assess the leaching behaviour of the elements. Powder X-ray diffraction (PXRD) and X-ray fluorescence (XRF) were used to determine the mineralization of the soil. The structural features of the soil were determined using Fourier Transform Infrared spectroscopy (FTIR) and the element content was determined using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). The point of zero charge (PZC) of the soil was found to be 8.3 and the cation exchange capacity (CEC) of 51.6 meq/ 100g. In the absence of fertilisers and plant exudates, the soil exhibited a similar high adsorption for elements at all initial concentrations by all the elements. Most (> 90%) of the elements were adsorbed within the first 3 minutes of contact with the soil. Langmuir, Freundlich and Dubinin-Radushkevich adsorption isotherms were used to describe the experimental data for the elements. Kinetic rates were modelled using pseudo first-order and pseudo second-order equations. Pseudo v second-order gave the best fit for all the elements (R2 >0.999) indicating chemisorption. The effect of pH on Cd and Cu was insignificant however, the adsorption of Cr decreased with pH. The presence of competing ions decreased the adsorption of cadmium more than that of the other analyte elements. The soil was generally effective in adsorbing and retaining the elements. However, the retention was highly dependent on elemental speciation and prevailing conditions e.g. pH (as in the case of Cu and Cr). Such changes in conditions would have implications for groundwater quality. The effect of plant exudates and EDTA was studied and the results showed that low molecular weight organic acids (LMWOAs) viz acetic acid (AA), citric acid (CA) and oxalic acid (OA) and EDTA significantly (p < 0.05) decreased the adsorption capacity of the elements onto the agricultural soil. AA had the least effect on the adsorption capacity of the elements whereas OA and EDTA strongly prevented the adsorption of the elements. Moreover, some of the elements which were already in the soil including those which were not under study such as Ca and Mg were desorbed from the soil by OA and EDTA. Thus, the mobility of the elements was increased by the presence of plant exudates, increasing groundwater contamination and consequently threatening the health of living organisms. Agrochemicals such as fertilisers, stabilizers and pesticides are constantly applied to agricultural soils to improve the fertility of the soil for better crop production however; their presence may affect the mobility and bioavailability of elements in the soil. The effect of ammonium nitrate and ammonium phosphate as well as calcium chloride on the adsorption of Cd, Cu and Cr onto an agricultural soil was studied. The effects of initial concentrations of the elements (5 – 50 mg/L), concentrations of fertilisers (0.01 – 0.1 mol/L) and pH (3 - 8) on the adsorption of Cd, Cu and Cr were studied. The initial concentration of the elements and the concentration of fertilisers had no significant effect (p > 0.05) on the adsorption capacities of Cu and Cr at pH 5. But, ammonium nitrate and calcium chloride decreased the adsorption capacity of Cd. The adsorption of Cd onto the soil was reduced as the concentration of fertilisers increased. The adsorption of Cd was lower than that of Cu and Cr at all pH values. The agricultural soil was found to vi be an effective adsorbent in preventing the mobility of Cu and Cr in the presence of fertilisers but not for Cd whose adsorption was significantly affected by the presence of ammonium nitrate and calcium chloride. A continuous flow fixed-bed column script with specified conditions simulating the natural environment was utilised in PHREEQC for column studies. The geochemical computer model PHREEQC can simulate solute transport in soil surfaces. The effect of initial concentration (100 and 300 mg/L) of the elements, column bed depth (5 and 10 cm) and pH (3, 5, 7 and 10) were considered in this study. The adsorption capacity was affected by initial concentration of the elements since the breakthrough curves at higher analyte concentrations were reached at lower pore volumes than at low concentrations. This can be attributed to the fast occupation of active sites of the soil at higher concentrations. The results from PHREEQC indicated that the conditions used would lead to the oxidation of Cr3+ to Cr6+ leading to the formation of HCrO4- and Cr2O72- which were not favoured for adsorption by soil surfaces due to high solubility. This could have potential implications on the quality of groundwater in regions with similar conditions. Thus, the leaching of Cr6+ onto the agricultural soil will be high in areas where remediation techniques are not applied. The changing of bed depth from 5 to 10 cm did not have an effect on the adsorption of the elements. The ability of the soil surfaces to adsorb Cd and Cu even at lower bed depth implies that the soil will be effective in preventing the leaching of the elements to groundwater due to strong surface interactions of the elements with the soil. The results from PHREEQC showed that the adsorption of Cd and Cr onto the soil surface was not affected by pH. The results for Cr were contradicting with those obtained from laboratory experiments which could be due to the conditions used in PHREEQC. The change in the speciation of Cu at basic conditions decreased the ability of Cu adsorption onto the soil surfaces. The Cu2+ was converted to Cu(OH)2 which were large in size and thus only a small amount could be adsorbed since the other adsorption sites were covered by the large species. This research had notable outputs in the form of publications which will form an important repository of information.
LG2017

The mining industry produces vast quantities of overburden and mill tailings. In many instances the disposal of these wastes on the Earth's surface have caused local, and occasionally even regional, water resources to become contaminated. Contamination typically arises from the oxidation of metal sulfide minerals contained within these wastes. Upon oxidation these minerals release sulfate, their associated metal cations and acidity into solution. This study investigated the potential for groundwater contamination arising from a Pb/Zn tailings impoundment in the North West Province of South Africa (Pering Mine). The tailings is composed predominantly of dolomite, which imparts to the material an alkaline pH and a high acid buffering capacity. Acid-base accounting (ABA) established that the capacity of the tailings to buffer acidity surpasses any acid producing potential that could arise from pyrite (FeS2), galena (PbS) and sphalerite (ZnS) oxidation. These minerals account for about 3 to 6% of the tailings by mass. Total elemental analysis (XRF) showed that the material has high total concentrations of Fe (19083 mg kg-I), Zn (5481 mg kg-I), Pb (398 mg kg-I), S (15400 mg kg-I), Al (9152 mg kg-I) and Mn (29102 mg kg-I). Only a very small fraction of this, however, was soluble under saturated conditions. An estimation of potentially available concentrations, using the DTPA extraction method, indicated that high concentrations of Zn (1056 mg kg-I), and moderate concentrations of Pb (27.3 mg kg-I) and Cu (6.01 mg kg-I) could potentially be available to cause contamination. A number of leaching experiments were undertaken to accurately quantify the release of elements from the tailings material. These experiments were aimed at determining the potential for groundwater contamination and also provided a means whereby the long-term release of contaminants could be modelled using the convection-dispersion equation for solute transport. Four leaching treatments were investigated. Two consisted of using distilled water under intermittent and continuous flow, while a third used intermittent flow of deoxygenated distilled water to assess leaching under conditions of reduced oxygen. The.mobilisation of potential contaminants under a worst case scenario was assessed by means of leaching with an acetic acid solution at pH 2.88 (after the US Environmental Protection Agency's toxicity characteristic leaching procedure). The acid buffering potential of the tailings was considerable. Even after 8 months of weekly leaching with 1 pore volume of acetic acid solution the pH of the effluent was maintained above pH 5.90. The protracted acidity caused very high concentrations of Pb, Zn, Mu, Ca, Mg, Hg and S to be released into solution. Leaching the tailings with distilled water also caused the effluent to have noticeable traces of contamination, most importantly from S, Mg, Mu and Zn. In many instances concentrations significantly exceeded guideline values for South African drinking water. Modelling solute transport with the convectiondispersion equation predicted that sol- and Mu contamination could persist for a very long period of time. (±700 years under continuous saturated leaching), while Mg and Zn concentrations would most likely exceed recommended limits for a much shorter period of time (±300 years under the same conditions). In light of the various column leaching experiments it was concluded that seepage from the Pering tailings impoundment could cause groundwater contamination. A drill-rig and coring system were used to collect both tailings and pore-water samples from eight boreholes spread out across the tailings impoundment. These investigations showed that most of the impoundment was aerobic (Eh ranged from +323 to +454 mY) and alkaline (pH 8.0 to 9.5). This chemical environment favours sulfide oxidation and as a consequence high concentrations of S have been released into the pore-water of the impoundment (S concentrations ranged from 211 to 1221 mg r l ). The acidity released as a by-product of sulfide oxidation was being buffered by dolomite dissolution, which in turn was releasing high concentrations of Mg (175 to 917 mg r l ) and Ca (62.6 to 247 mg r l ) into solution. Metal concentrations in the pore-water were low as a result of the strong metal sorbing capacity of the tailings and possible secondary precipitation. The only metal which significantly exceeded recommended limits throughout the impoundment was Hg (concentrations were between 100 and 6000 times the recommended limit of 0.001 mg r l ). Under the current geochemical conditions it is expected that Hg, S and Mg will likely pose the greatest threat to groundwater. The main concerns associated with mine tailings are that of mine drainage and dust blow off..In order to eradicate the latter problem, the tailings impoundment at Pering Mine was covered with a layer of rocks. Modelling the water balance of the impoundment using the computer model HYDRUS-2D showed that the rock cladding has potentially increased the volume of drainage water seeping from the impoundment. In light of the leaching experiments and field work, which proved that water passing through the tailings became enriched with various potentially toxic elements, it is expected that the problem of groundwater contamination around Pering Mine has been further exacerbated by the rock cladding. It was therefore concluded that there would be a strong likelihood of groundwater contamination in the vicinity of the mine.
Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2006.

The original aims of this project were to investigate the potential for phytoremediation, with emphasis on metal accumulation, of three contrasting industrial processing wastes. These were tailings material (PT) from the decommissioned Pering Pb/Zn Mine (Reivilo, North West Province, South Africa (SA)), smelter slag (SS) from the Samancor Mnsmelter (Meyerton, Gauteng, SA) and electro-winning waste (EW) from MMC (Nelspruit, Mpumalanga, SA). It became evident, however, early in the project, that the use of metal hyperaccumulating plants was not a viable technology for these wastes. The project objectives were thus adapted to investigate alternative remedial technologies. The use of endemic and adapted grass species was investigated to revegetate the PT. In addition, chemically-enhanced phytoremediation was investigated to induce metal hyperaccumulation by grasses grown in the PT (Part 1). Revegetation of the SS and EW were not considered feasible, thus land disposal of these two Mn-rich processing wastes was investigated (Part 2). Part 1 - Revegetation of tailings from Pering Mine The PT was found to be alkaline (pH > 8.0), and consisted mainly of finely crushed dolomite. It was generally nutrient poor with high amounts of readily extractable Zn. It also had a very high P-sorption capacity. Seven grass species (Andropogon eucomus Nees; Cenchrus ciliaris L.; Cymbopogon plurinodis Stapf ex Burtt Davy; Digitaria eriantha Steud; Eragrostis superba Peyr; Eragrostis tef (Zucc.) Trotter and Fingeruthia africana Lehm) were grown in PT treated with different rates of inorganic fertiliser under glasshouse conditions. The fertiliser was applied at rates equivalent to 100 kg N, 150 kg P and 100 kg K ha-1 (full), half the full rate (half) and no fertiliser (0). Seed of C. ciliaris, C. plurinodis, D. eriantha, E. superba and F. africana were collected from Pering Mine. Seed of A. eucomus was collected from the tailings dam of an abandoned chrysotile asbestos mine. These were germinated in seedling trays and replanted into the pots. A commercial variety of E. tef was tested, but due to poor survival this species was subsequently excluded. The foliage and root biomass of the grasses and concentrations of Ca, Cu, Fe, K, Mg, Mn, Pb and Zn in the foliage were determined. The yield of all the grasses increased with an increase in fertiliser rate, with a significant species by fertiliser interaction (p = 0.002). The highest yield was measured for C ciliaris, followed by D. eriantha (4.02 and 3.43 g porI, respectively), at the full fertiliser application rate. Cymbopogon plurinodis was the third highest yielding species, while the yields of E. superba and F. africana were similar. There were positive linear correlations between foliage yield and fertiliser application rate for all grasses. The root biomass of the grasses also increased with an increase in fertiliser application rate. The interaction between grass species and fertiliser level had a non-significant (p = 0.085) effect on the yield of grasses, though there were significant individual effects of species (p < 0.001) and fertiliser (p < 0.001). Digitaria eriantha had the highest root biomass at each fertiliser application rate, followed by C plurinodis and C ciliaris. Similarly to foliage yield, there were positive linear correlations between root biomass and fertiliser application level. Positive, linear correlations were found between foliage yield and root biomass, though the strength of these varied. The weakest correlation was found for D. eriantha (R2 = 0.42) but this was attributed to a moderately high variance in foliage yield and roots becoming potbound. Generally, nutrient concentrations were within adequacy ranges reported in the literature, except for P concentrations. This was attributed to the high P-sorption capacity of the PT. Zinc concentrations were higher than the recommended range for grasses, and also increased with an increase in fertiliser application rate. This was attributed to the high available Zn concentrations in the PT and improved growth of the grasses at higher fertiliser application rates. It was recommended that C ciliaris and D. eriantha be used for revegetation due to high biomass production and that E. superba be used because of rapid growth rate and high self-propagation potential. Both C plurinodis and F. africana can also be used but are slower to establish, while A. eucomus was not a suitable species for revegetation of the PT. Inorganic fertiliser improved the growth of all these species and is recommended for the initial establishment of the grasses. An experiment was conducted to investigate the potential of inducing metal hyperaccumulation in three grass species (C ciliaris, D. eriantha and E. superba) grown in the PT. Grasses were grown in fertilised tailings for six weeks, then either ethylenediaminetetraacetic acid (EDTA) or diethylentriaminepentaacetic acid (DTPA) was added to the pots at rates of 0, 0.25, 0.5, 1 and 2 g kg-I. Grasses were allowed to grow for an additional week before harvesting. The concentrations of Cu, Pb and Zn were determined in the foliage. The interactive effect of species and chelating agent on the uptake of Cu was marginally significant (p = 0.042) and non-significant for Pb and Zn (p = 0.14 and 0.73, respectively). While the addition of the chelating agents resulted in an increase in Pb uptake by the grasses, it did not induce metal hyperaccumulation in the grasses. This was attributed to the ineffectiveness of the chelating agents in the PT in the presence of competing base cations (mainly Ca). The use of this technology was not recommended. Part 2 - Land disposal of Mn-rich processing wastes Chemical characterisation of the SS showed that it was an alkaline (pH > 9.5), Mn-rich silicate (glaucochroite), that generally·had low amounts of soluble and readily extractable metals. Acidic extractants removed high amounts of Mn, Ca and Mg, attributed to the dissolution of the silicate mineral. The EW was highly saline (saturated paste EC = 6 780 mS m,l) with a near-neutral pH. It had high amounts of soluble Mu, NHt+, S, Mg, Ca and Co. The primary minerals were magnetite, jacobsite (MnFe204) and gypsum. The effect of SS and EW on selected chemical properties of six soils was investigated by means of an incubation experiment, and their effect on the yield and element uptake by ryegrass was investigated in selected soils under glasshouse conditions. Five A-horizons (Bonheim (Ba), Hutton (Hu), lnanda (la), Shortlands (Sd) and Valsrivier (Va» and an Ehorizon (Longlands (Lo» were treated with SS at rates of 30, 60, 120,240 and 480 g kg'l and EW at rates of20, 40,80,160 and 320 g kg'l. Soils were incubated at field capacity at 24 QC and sampled periodically over 252 days. The soil pH, both immediately and over time, increased, while exchangeable acidity decreased after the addition of SS to the soils. The pH at the high rates of SS tended to be very high (about 8). The electrical conductivity (EC) of the soils also increased with an increase in SS application rates and over time. The most marked changes tended to occur in the more acidic soils (e.g. la). In the soils treated with EW, there was generally an increase in the pH of the acid soils (e.g. la) while in the more alkaline soils the pH tended to decrease (e.g. Va), immediately after waste application. There was a general decrease in pH over time, with a concurrent increase in exchangeable acidity, due to nitrification processes. The EC of all the soils increased sharply with an increase in EW application rate, attributed to the very saline nature of the EW. Water-soluble Mn concentrations in the soils treated with SS tended to be below measurable limits, except in the acid la. Iron concentrations decreased with an increase in SS application rate and over time for all soils. The water-soluble concentrations of Mn, Ca, Mg and S increased sharply with an increase in EW application rate in all soils. There was also a general increase in Mn concentrations over time. Iron concentrations tended to be low in the EW-treated soils, while Co concentrations increased as EW application rate increased. Exchangeable (EX, 0.05 M CaCh-extractable) concentrations of Fe, Co, Cu, Zn and Ni were low in the SS-treated soils. The concentrations of EX-Mn tended to increase with an increase in SS application rate in the la soil, but generally decreased in the other soils. There was also a decrease over time, attributed to the high pH leading to immobilisation of Mn. The EX-metal concentrations of the EW-treated soils were generally low, except for Mn. The concentrations of EX-Mn increased sharply as EW application rate increased. The contribution of EX-Mn was calculated to range from 209 to 3 340 mg Mn for EW rates of 20 to 320 g kg-I, respectively. In the Lo soil the expected amount of Mn was extracted at the different EW application rates. In the other soils the EX-Mn concentrations were typically higher than expected. This was attributed primarily to the dissolution ofMn from the EW due to the interaction between soil organic matter and the EW. There was generally an increase in EX-Mn concentrations over time, attributed to the decrease in pH of the soils treated with EW. The above-ground biomass production of ryegrass grown in Lo and Hu soils treated with SS increased at low application rates, but decreased again at the highest rates. The reduction in yield was attributed to an increase in soil pH leading to trace nutrient deficiencies. At the lower SS application rates, nutrient concentrations of the ryegrass tended to be within typical adequate ranges reported in the literature. Of concern was the elevated Mn concentration in the ryegrass foliage, though no toxicity symptoms were seen. This was attributed to the dissolution of the silicate mineral due to soil acidification processes and the possible ameliorating effect of high Ca and Si concentrations on Mn toxicity. The growth of ryegrass was generally poor in the Hu soil treated with EW and it did not survive beyond germination in the Lo soil treated with EW. In the Hu soil plants grew well in the 20 and 40 g kg-I EW treatments, but died at the higher rates. In both cases mortality was thought to be due to the high salinity that resulted in toxicity and osmotic stress in the newly germinated seedlings. The improved growth at the lower rates ofEW, in the Hu soil, was attributed mainly to increased N availability. The concentrations of Mn in the foliage were elevated in the soils treated with EW. A pot experiment was conducted to test the effect of applying either humic acid (HA) or compost (at a rate of 20 g kg-I) with lime (at rates of 0, 5 and 10 Mg ha-I) on the growth and nutrient uptake of ryegrass grown in the Hu soil treated with EW at rates of 0, 10, 20 and 40 g kg-I. A basal P-fertiliser was also applied in this experiment. The highest yields were measured in the treatments receiving either HA or compost at the highest application rate ofEW. The addition oflime did not improve the yield of the HA treatments, but did in the compost treatments. Generally, nutrient concentrations were adequate. The Mn concentrations were markedly lower than expected, and this was attributed to the formation of insoluble Mn-P compounds due to the addition of fertiliser. The effect of either HA or compost on Mn concentrations was not marked, but lime reduced Mn uptake. A leaching column experiment showed that, generally, the Mn was not readily leached through a simulated soil profile, though the addition of compost may enhance mobility. There was also evidence to indicate an increase in salinity and that Co concentrations of the leachate may be a problem. These data suggest that soil organic matter may be a very important factor in determining the release of Mn from the wastes, notably the EW. The land disposal of the SS and EW was not recommended at the rates investigated here, as both showed the potential for Mn accumulation in above-ground foliage, even at low application rates, while high application rates negatively impacted on plant growth. It appears that P-compounds may be beneficial in reducing Mn availability in the EW, but further testing is required.
Thesis (Ph.D.)-University of KwaZulu-Natal, Pietermaritzburg, 2007.