Mineralogical and geochemical characteristics of metallurgical wastes from the Cu-Co smelters situated in the Zambian Copperbelt have been investigated. A number of instrumental analytical methods (XRD, SEM/EDS, EPMA, TEM/EDS) has been used to identify primary and secondary phases in smelter slags and dusts. A set of leaching experiments (CEN/TS 14997 pH-static test, EN 12457 batch test) in combination with geochemical modelling has been performed, with the emphasis on the leaching behaviour of potential contaminants and their release as a function of the pH. The effect of sample preparation on metal leachability from slag was also evaluated, considering the grain size reduction required by the standardised leaching protocols. Environmental and health risk assessments of the dust samples have been performed. It was shown that the main carriers of metals in the studied slags were Cu sulphides (bornite, digenite, chalcocite), Co sulphides (cobaltpentlandite), Co-bearing intermetallic phases and alloys. Copper and cobalt were detected in major silicates and spinels, substituting for Fe or Mg in their structures, and in glass. The presence of secondary metal-bearing phases observed on the slag surfaces indicated the reactivity of the slags on contact with water/atmosphere. It was reported that in...

Hazardous waste substances are solid, semi-solid or non-aqueous liquids that exhibit characteristics of corrosivity, reactivity, ignitability, toxicity and infectious property. Major available options for management of hazardous waste include direct disposal into landfill or chemical treatment/stabilization of wastes prior to landfill disposal. Hazardous wastes are accepted for direct disposal in engineered landfills if they conform to the chemical concentration limit criterion (determined by water leach test followed by estimation of the concentration of the contaminant) and compressive strength (the material should have compressive strength > 50 kPa) criterion. Lead is classified as extremely toxic metal. Elevated levels of lead in water (surface and ground water) primarily arise from industrial discharges, and aerial deposition. During its residence in surface water bodies, the lead may interact detrimentally with aquatic life or be abstracted into public water supplies. According to National drinking water standards, the permissible limit of lead in drinking water is 0.05 mg/l. Deposition of air-borne lead, disposal of sewage sludge on land and disposal of industrial effluents on lands are major sources of lead contamination of soils. When incorporated in soil, lead is of very low mobility. Lead retained in soils can be slowly leached to the groundwater thereby impacting human health if consumed for potable needs. Alternatively lead deposited in soils can be absorbed by vegetation (crops/trees) and can impact human health on their consumption. Given the negative impacts of lead contamination on human health, the strong affinity of soils to retain deposited lead and the possible release for human consumption, this thesis focuses on characterization and chemical stabilization of artificially lead contaminated soils in the context of their disposal in hazardous waste landfills. The main objectives of the thesis are: characterize artificially lead contaminated soils for water leachability of lead and undrained strength characteristics as per CPCB (Central Pollution Control Board) guidelines in the context of disposal criteria in hazardous waste landfills. Artificially lead contaminated soils in compacted and slurry states are used in the thesis. Red soil (from Bangalore District, Karnataka) and river sand are used in the preparation of compacted and slurry specimens. The red soil and red soil-sand specimens are artificially contaminated in the laboratory by employing aqueous lead salt solutions as remolding fluids. Lead concentrations of 160 to 10000 mg/l are used in this study. The results of characterization studies with artificially lead contaminated soils help identify contaminated soil materials that require chemical stabilization prior to disposal into engineered landfills. Based on the results of characterization studies with artificially lead contaminated soils, lime stabilization coupled with steam curing technique is resorted to immobilize lead in the red soil-sand slurry specimens and mobilize adequate undrained strength to meet the criteria for disposal of lead contaminated soils in hazardous landfills. After this first introductory chapter, a detailed review of literature is performed towards highlighting the need to undertake chemical stabilization of artificially lead contaminated soils in Chapter 2. Chapter 3 presents a detailed experimental program of the study. Chapter 4 presents the physico-chemical and mechanical characterization of the artificially lead contaminated soils. The ability of artificially contaminated soils to release (artificially added) lead during water leaching is explained using lead speciation results performed using the Visual MINTEQ program. Experimental results illustrated that contamination of compacted red soil and red soil + sand specimens with significant lead concentrations (21 to 1300 mg/kg) resulted in major fractions of the added lead being retained in the precipitated state. Results of water leach tests revealed that lead concentrations released in the water leachates are far less than (0.0011 to 0.48 mg/l) limits prescribed by CPCB (2 mg/l) for direct disposal of lead contaminated materials into hazardous waste landfills. Unconfined compressive strengths developed by the lead contaminated red soil and red soil-sand specimens were significantly higher (100-2700 kPa) than the strength requirement (> 50 kPa) for direct disposal of hazardous wastes in engineered landfills. Lead contamination did not affect the unconfined compression strengths of the specimens as matric suction prevalent in the unsaturated compacted soils had an overriding influence on the cementation bond strength created by the lead precipitates. Visual Minteq tool was helpful in predicting the amount of added lead that was converted to insoluble precipitate form. However the amounts of water leachable lead determined experimentally and predicted by Visual Minteq were very different-Visual Minteq predicted much higher amounts of water leachable lead than experimentally determined. Experimental results revealed that the levels of lead released by the red soil-sand slurries in water leach tests were in excess (13 to 36 mg/l) of the permissible lead concentration (2 mg/l) for direct disposal of hazardous waste in landfills. Owing to water contents generally being in excess of their liquid limit water contents (w/wL ratio > 1) the slurry specimens exhibited undrained strengths below 1 kPa. Lime stabilization and steam curing of the contaminated slurry specimens was therefore resorted to control the leachibility of lead and increase undrained strengths to acceptable limits. Chapter 5 deals with lime stabilization of artificially contaminated slurries that do not meet the leachate quality (lead concentration in water < 2 mg/l) or compressive strength (> 50 kPa). Procedures are evolved for lime stabilization of such artificially contaminated soils to meet both the water leachate quality and compressive strength criteria. Lime stabilization together with steam curing of the lead contaminated slurry specimens effectively immobilized the added lead (2500 mg/kg) and imparted adequate compressive strengths to the contaminated red soil-sand slurry specimens. The lime stabilized contaminated specimens released marginal lead concentrations (0.03 to 0.45 mg/l) in the water leach; these values are much lower than permissible limit (2 mg/l) for disposal in hazardous landfills or values exhibited by the unstabilized specimens (13 to 38 mg/l). Lime addition rendered the contaminated specimens strongly alkaline (pH values ranged between 10.68 and 11.66). Combination of the experimental and Visual Minteq results suggested that precipitation of lead as hydrocerrusite in the alkaline environments (pH 10.68 to 11.95) is not the sole factor for marginal release of lead in water leach tests of the 4, 7 and 10 % lime stabilized contaminated specimens. It is possible that fraction of lead ions are entrapped within the cemented soil matrix. Water leach tests performed at range of pH values (pH 2.5 to 9.6) with 7 % lime stabilized specimens suggested that immobilization of lead as hydrocerrusite or as entrapment in the cemented soil mass in the lime stabilized specimens is practically irreversible even on exposure to extreme pH conditions. The lime stabilized contaminated specimens developed unconfined compressive strengths ranging from 100 kPa (4 % lime stabilized 40 % red soil-60 % sand specimen) to 1000 kPa (10 % lime stabilized 100 % red soil specimen). The significant growth of compressive strength upon lime stabilization is attributed to growth of inter-particle cementation bonds by the CAH (calcium aluminate hydrate) and CSH (calcium silicate hydrate) compounds formed by lime-clay reactions, slight reduction in void ratios and growth of strong inter-particle cementation bonds the during steam curing at 800C. The results of this thesis bring out a procedure to immobilize high concentrations of lead and develop adequate compressive strength of lead contaminated slurry specimens by lime stabilization + steam curing technique. The red soil acted as pozzolana in reactions with lime, while, steam curing accelerated the lime-soil reactions. The procedure can be extended to non-organic slurry wastes that are devoid of pozzolanic material (example, lead contaminated smelting sands). In slurry wastes devoid of pozzolana, materials such as fly ash can be added and the reactions between lime and fly ash would immobilize lead + develop adequate compressive strength. Also, similar to the methodology being adaptable for any non-organic slurries, it can also be extended to other toxic metal bearing wastes, example, zinc, cadmium and nickel.

L'intensification des activités industrielles et les besoins en énergie font des hydrocarbures pétroliers (HP) un enjeu majeur mondial mais augmentent aussi considérablement les risques environnementaux dans divers écosystèmes. La phytoremédiation est une phytotechnologie qui a fait ses preuves en tant que solution verte pour faire face aux contaminations des sols par des HP. La phytoremédiation des sols contaminés par les HP repose principalement sur l’activité des communautés microbiennes associées aux racines des plantes au niveau de la rhizosphère, qui peuvent non seulement favoriser la croissance des plantes hôtes mais aussi augmenter leur tolérance à divers stress biotiques et abiotiques. Parmi les défis majeurs de la phytoremédiation des sols contaminés par les HP, on compte la forte toxicité de certains composés des HP qui entravent la croissance des plantes et par conséquent l’efficacité de la phytoremédiation. Cependant, la croissance des plantes peut être positivement stimulée par la présence de rhizobactéries favorisant leur croissance (PGPR) qui sont capables d'atténuer le stress des plantes par divers mécanismes. Dans cette thèse, un total de 438 bactéries PGPR dégradant les hydrocarbures pétroliers, ont été isolées de la rhizosphère et du sol de deux espèces de plantes, Salix purpurea et Eleocharis obusta, dans un site d'une ancienne raffinerie pétrochimique à Varennes, QC, Canada. Les isolats bactériens ont été classés en 62 genres, appartenant aux phylums Actinobacteria, Bacteroidetes, Firmicutes et aux sous-groupes Alpha-, Beta- et Gamma-Proteobacteria. De plus, cette collection de cultures contient 438 isolats bactériens avec de multiples caractéristiques de dégradation et de stimulation de croissance (PGPR), représentant une diversité fonctionnelle de dégradation des HP et de caractéristiques PGPR qui pourraient être utilisées dans la phytoremédiation assistée par les bactéries, des sols contaminés par les HP. Parmi ces 438 isolats bactériens, 50 isolats représentant une large diversité taxonomique, ont été sélectionnées pour une caractérisation approfondie supplémentaire concernant leur capacité à favoriser la croissance des plantes en présence de différentes concentrations de n-hexadécane (0%, 1%, 2%, 3%) dans des conditions contrôlées. Les résultats ont indiqué que les isolats bactériens Nocardia sp. (WB46), Pseudomonas plecoglossicida (ET27), Stenotrophomonas pavanii (EB31), Bacillus megaterium (WT10) et Gordonia amicalis (WT12) ont significativement augmenté la croissance des plantes cultivées dans 3% de n-hexadécane par rapport au traitement témoin. De plus, ces isolats possèdent plusieurs traits favorisant la croissance des plantes (PGPR) tels que l'activité 1-aminocyclopropane-1-carboxylate (ACC) désaminase (ACCD), la production d'acide indole-3-acétique (IAA) et la fixation de l'azote. De plus, ces isolats étaient capables d'utiliser le n-hexadécane comme seule source de carbone et possédaient des gènes cataboliques liés à la dégradation des hydrocarbures tels que le gène de l'alcane monooxygénase (alkB), le cytochrome P450 hydroxylase (CYP153) et le gène de la naphtalène dioxygénase (nah1). Nocardia sp. isolate WB46, a été sélectionné pour le séquençage de son génome afin de déterminer sa diversité génétique et fonctionnelle relatives à la dégradation des HP et les potentiels PGPR. Les résultats ont indiqué que, sur la base des analyses du gène de l'ARNr 16S, l'hybridation ADN-ADN in silico (DDH) et l'identité moyenne des nucléotides (ANI), Nocardia sp. isolate WB46 représente une nouvelle espèce bactérienne. De plus, l'annotation fonctionnelle de son génome révèle que celui-ci contient de nombreux gènes responsables de la dégradation des hydrocarbures pétroliers tels que l'alcane 1-monooxygénase (alkB) et la naphtalène dioxygénase (ndo) ainsi que d'autres gènes liés à ses potentiels PGPR. En conclusion, la rhizosphère des espèces S. purpurea et E. obusta poussant dans un site fortement pollué par les HP représente un biotope diversifié et comprenant des bactéries PGPR avec de multiples potentiels de dégradation des HP. De plus, plusieurs isolats bactériens tels que Nocardia sp. (WB46), Pseudomonas plecoglossicida (ET27) et Stenotrophomonas pavanii (EB31) démontrent un potentiel d'utilisation comme bioinoculants pour de futures études de phytoremédiation à grande échelle. / Petroleum hydrocarbons (PHCs), as a result of intensification of industrial activities, are a global environmental issue especially in soil environments. Phytoremediation represents an ideal solution to tackle this global crisis. Phytoremediation of PHC-contaminated soils proceeds mainly through the activities of microbial communities that colonize the plant rhizosphere which might promote host plants growth and increase its tolerance to various biotic and abiotic stresses. A main challenge in phytoremediation of PHC-contaminated soils is the high toxicity of PHCs which hinder plant growth and reduce the efficiency of phytoremediation. However, plant growth may be positively stimulated by the presence of plant growth-promoting rhizobacteria (PGPR) that are able to alleviate stresses in plants through various mechanisms. In this thesis, a total of 438 petroleum hydrocarbons degrading-PGPR bacterial isolates were recovered from the rhizosphere and the surrounding bulk soil of Salix purpurea and Eleocharis obusta plants from the site of a former petrochemical plant in Varennes, QC, Canada. Bacterial isolates were classified into 62 genera, belonging to the phyla Actinobacteria, Bacteroidetes, Firmicutes and the Alpha, Beta and Gamma-subgroups of Proteobacteria. Additionally, this culture collection holds 438 bacterial isolates with multiple degradative and PGP features, representing a rich reservoir of metabolically versatile PGPR-PHC degraders that could be used in holistic, bacterial-aided phytomanagement of PHC-contaminated soils. Among the above 438 bacterial isolates, 50 bacterial strains representing a wide phylogenetic range were selected for an additional in-depth characterization regarding their ability to promote plant growth under the presence of different concentrations of n-hexadecane (0%, 1%, 2%, 3%) under gnotobiotic conditions. Results indicated that bacterial isolates Nocardia sp. (WB46), Pseudomonas plecoglossicida (ET27), Stenotrophomonas pavanii (EB31), Bacillus megaterium (WT10) and Gordonia amicalis (WT12) significantly increased the growth of plants grown in 3% n-hexadecane compared with the control treatment. Additionally, these isolates possess several plant-growth-promoting (PGP) traits such as 1-aminocyclopropane-1-carboxylate (ACC) deaminase (ACCD) activity, indole-3-acetic acid (IAA) production and nitrogen fixation. Also, these isolates were able to use n-hexadecane as sole source of carbon and have catabolic genes related to hydrocarbon degradation such alkane monooxygenase (alkB) gene, the cytochrome P450 hydroxylase (CYP153) and the naphthalene dioxygenase (nah1) gene. The isolate that showed the highest growth stimulation of plants grown in 3% n-hexadecane under gnotobiotic conditions, Nocardia sp. isolate WB46, was selected for de novo genome sequencing to unveil its genetic versatility and the mechanisms of PHCs biodegradation and PGP potentials. Results indicated that based on the 16S rRNA gene analyses, in silico DNA-DNA hybridization (DDH) and average nucleotide identity (ANI) Nocardia sp. isolate WB46 is a new species. Additionally, the functional annotation of the genome of Nocardia sp. isolate WB46 reveals that its genome contains many genes responsible for petroleum hydrocarbon degradation such as alkane 1-monooxygenase (alkB) and naphthalene dioxygenase (ndo) as well as other genes related to its PGP potentials. In conclusion, S. purpurea and E. obusta growing in a site highly polluted with PHCs are rich reservoir of diverse PGPR with multiple PHC-degradation and PGP potentials. In addition, several bacterial isolates such as Nocardia sp. (WB46), Pseudomonas plecoglossicida (ET27) and Stenotrophomonas pavanii (EB31) demonstrate potential for use as bioinoculants in future large-scale phytoremediation studies.