The ability of alumino-silicate systems to immobilize hazardous compounds has been investigated since 1990s. The aim of this work is to develope alumino-silicate system (matrix) based on industrial waste products with ability to immobilize hazardous compounds (heavy metals). This ability of the matrix was confirmed by leaching tests based on the law 294/2005 Sb. Concentration of heavy metals in leachates was determined by ICP-MS method. Alumino-silicate system prepared in this work consists of high-temperature fly ash and blast furnace slag activated by mixture of alkaline activators (hydroxide and water glass). Matrixes were characterized by suitable analytic methods (XRD, SEM, FT-IR, DTA-TGA-EGA). The same analytic methods were used to describe the mechanism of immobilization of selected elements (Ba, Cu, Pb) in prepared systems.

Water contaminations by many pollutants, especially heavy metals such as Pb(II), Hg(II), Cu(II), Cd(II), and Cr(VI) pose many public health and environmental concerns as reported in the list of hazardous substances compiled by the US Environmental Protection Agency due to their high toxicity, refractory degradation, and ease of entering food chain. Adsorption by chelating resins is proven to be the most effective method for the extraction of metal ions from polluted and wastewater. However, traditional absorbents such as activated carbon, activated alumina, clay, zeolite, etc., show limited adsorption abilities for these heavy metal ions. The major goal of this thesis is to develop efficient and cost-effective adsorbents for the extraction of heavy metals from wastewater. This dissertation will focus on the development of four chemically modified high surface area adsorbents with accessible chelating sites for capturing and retaining toxic metal ions from polluted water. The first adsorbent, Nitrogen Doped Carboxylated Activated Carbon (ND-CAC), is prepared by a polymerization reaction between melamine and formaldehyde to form the melamine formaldehyde resin (MF-R) followed by carbonization at 800 oC under nitrogen atmosphere to form nitrogen doped carbon (ND-C), and finally oxidation to form the ND-CAC adsorbent. The ND-CAC adsorbent shows high adsorption capacities of 750.5, 250.5, 98.2 mg/g for the extraction of Pb(II), Hg(II), and Cr(VI), respectively from aqueous solutions with a high selectivity to Pb(II). The second adsorbent, Melamine Zirconium Phosphate (M-ZrP) is prepared by a precipitation reaction between Melamine Phosphate (MP) and ZrCl4 in an aqueous solution. The M-ZrP adsorbent is used for the removal of Pb(II), Hg(II), and Cd(II) with maximum adsorption capacities of 680.4, 119.0, and 60.0 mg/g, respectively with a high selectivity to Pb(II). The third adsorbent is chemically functionalized metal organic framework (UIO-66-IT) was prepared by post-synthetic modification using the chelating ligand 2-Imino-4-Thioburit. The adsorbent was used to extract Hg(II) and (HPO4)- ions from aqueous solutions and the results revealed exceptionally high adsorption capacities toward mercury and phosphate ions of 700 and 160 mg/g, placing it among the top functionalized MOF known for the high capacity of Hg(II) removal from aqueous solutions. The fourth adsorbent, Melamine Thiourea Partially Reduced Graphene Oxide (MT-PRGO) prepared by the amidation reaction between chemically modified graphene oxide and melamine thiourea, is used for the effective extraction of Hg(II), Co(II) and Cu(II) from polluted water. The MT-PRGO adsorbent shows exceptional selectivity for the extraction of Hg(II) with a capacity of 651 mg/g, placing it among the top of carbon-based materials known for the high capacity of Hg(II) removal from aqueous solutions. Desorption studies demonstrate that the new adsorbents ND-CAC, M-ZrP, UIO-66-IT, and MT-PRGO are easily regenerated with the desorption of the heavy metal ions Hg(II), Pb(II), Cd(II), and Cr(VI) reaching 99 % - 100 % recovery from their maximum sorption capacities using different eluents. Moreover, all prepared adsorbents showed tremendous abilities to clean contaminated water from toxic heavy metals at trace concentrations. That prove the ability of using them at water contamination level when the concentration of heavy metals is very low. The new adsorbents ND-CAC, M-ZrP, UIO-66-IT, and MT-PRGO are proposed as top performing remediation adsorbents for the extraction of the heavy metals Pb(II), Hg(II), Cd(II), Cr(VI), and (HPO4)- from waste and polluted water.

Philosophiae Doctor - PhD / The risk of increasing global pollution dictates the need to understand environmental processes and develop innovative ways to monitor pollution levels and address associated problems. In order to address this need, this study used a selection of plants leaves (Commelina benghalesis, Paspalum urvillei, Persicaria lapathifolia and Salix babylonica) as biomonitors to assess the state of the environment, more specifically the concentration of certain heavy metal pollutants (Cu, Zn, Fe, Ni, Pb and Cd) of river water and soils in the Eerste River catchment, Western Cape, South Africa.

The objective of this work was the development of an efficient adsorbent for irreversible immobilization of heavy metals in contaminated soils. The adsorbent was prepared by pillaring of montmorillonite with silica followed by grafting of a chelate ligand on its surface. Obtained adsorbent was mesoporous with high content of adsorption sites. Its structure was studied by BET adsorption of N2, dynamic light scattering, and scanning electron microscopy. The adsorption capacity of the organoclay was measured by its mixing with contaminated kaolin and soil samples and by analysis of heavy metal contents in leachate. Deionized water and 50% acetic acid were used for leaching of metals from the samples. As it was demonstrated by the experiments, the adsorbent was efficient in immobilization of heavy metals not only in neutral aqueous media but also in the presence of weak acid. As a result, the adsorbent can be used for reduction of heavy metal leaching from contaminated sites.

The objective of this work was the development of an efficient adsorbent for irreversible immobilization of heavy metals in contaminated soils. The adsorbent was prepared by pillaring of montmorillonite with silica followed by grafting of a chelate ligand on its surface. Obtained adsorbent was mesoporous with high content of adsorption sites. Its structure was studied by BET adsorption of N2, dynamic light scattering, and scanning electron microscopy. The adsorption capacity of the organoclay was measured by its mixing with contaminated kaolin and soil samples and by analysis of heavy metal contents in leachate. Deionized water and 50% acetic acid were used for leaching of metals from the samples. As it was demonstrated by the experiments, the adsorbent was efficient in immobilization of heavy metals not only in neutral aqueous media but also in the presence of weak acid. As a result, the adsorbent can be used for reduction of heavy metal leaching from contaminated sites.

La pollution des eaux usées par les éléments métalliques présents à l’état de traces et les cholorophénols pose un problème majeur pour l’environnement et la santé humaine. Cette étude concerne la synthèse d’argiles organophiles et de zéolithes à partir d’argiles naturelles prélevées en Tunisie et leurs applications pour l’adsorption respectivement des chlorophénols et des cations métalliques (Pb2+, Cd2+).Sur le plan de la synthèse d’argiles organophiles, une argile de type smectitique a été modifiée en utilisant le tensio-actif HDTMA. Cette argile organophile a été utilisée pour l’adsorption du 3-chlorophénol et du 4-chlorophénol. L’étude des isothermes et de la calorimétrie d’adsorption ont prouvé l’efficacité de cette argile organophile pour l’adsorption des deux chlorophénols.Des zéolithes ont été préparées à partir d’une argile naturelle composée de kaolinite, d’illite et de quartz. Ces zéolithes ont été utilisées pour l’adsorption des éléments métalliques tels que la cadmium (Cd2+) et le plomb (Pb2+) . Les cinétiques et les isothermes d’adsorption de Cd2+ et Pb2+ sur les zéolithes synthétisées (CAN, ANA, mélange Faujasite (FAU), néphéline et quartz), une cancrinite naturelle, une zéolithe commerciale (FAU 13X) et l’argile de départ ont été étudiées à 25°C en utilisant la méthode des restes. Une étude calorimétrique a été faite pour mieux comprendre les phénomènes mis en jeu lors de l’adsorption. La cinétique d’adsorption est très rapide. Une meilleure affinité est obtenue pour les zéolithes. / This study concerns the synthesis of zeolites and organophilic clays from clay and their applications for the adsorption of metallic elements (Pb2+, Cd2+) and chlorophenols.In terms of the synthesis of organophilic clays, a smectite clay was modified using the HDTMA surfactant. This organophilic clay was used for the adsorption of 3-chlorophenol and 4-chlorophenol. The study of isotherms and adsorption calorimetry have proved the effectiveness of this organophilic clay for the adsorption of the two chlorophenols.By hydrothermal high-pressure synthesis of zeolites, from natural clay composed of a fraction of kaolinite, illite and quartz, two types of zeolites were synthesized with good purity, a cancrinite (CAN) type zeolite and the other analcime (ANA) type; other type of zeolite was synthesized such as faujasite 13X but the purity and reproducibility was limited.These three types of zeolite (CAN, ANA and FAU 13X) were tested for the adsorption of Pb (II) and Cd (II). A better affinity of the zeolites synthesized than the starting clay with respect to the two metallic cations (Pb (II) and Cd (II)). The study of the adsorption kinetics of Pb (II) and Cd (II) showed rapid adsorption of the two metallic cations studied on the different types of zeolites. The results proved that the synthesized zeolites were a very promising materials for the adsorption and removal of heavy metals in water.

Algae are microscopic organisms with a great potential to produce biomass and lipids at productivities several times higher than terrestrial crops. To grow, these organisms consume carbon dioxide (CO2), a greenhouse gas. This gas, emitted primarily by power plants after coal burning, can be effectively used for algae production, thus resulting in CO2 remediation and biomass beneficial utilization as feedstuff, industrial filler and biodiesel feedstock. However, since coal is a fuel mined from the earth’s crust, it contains heavy metals that are released during coal burning and inevitably enter the algal cultivation system, contaminating the water were algae is grown, the algal biomass and the products derived from such biomass. The distribution of heavy metals from flue gas in algal cultivation systems is unknown, yet necessary to advance this industry. This study focused on quantifying the distribution and effects that ten coal-derived heavy metals (Cu, Co, Zn, Pb, As, Se, Cr, Hg, Ni and Cd) will have on algae strain Scenedesmus obliquus and on the potential products derived from this algae.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17881号 / 工博第3790号 / 新制||工||1580(附属図書館) / 30701 / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 米田 稔, 教授 田中 宏明, 教授 清水 芳久 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.

Mining activities, as essential as they are for our economy and our society, bring pollutants such as acid mine drainage (AMD) which contains dissolved metal(loid)s into the environment. There are different technologies currently being practiced to treat AMD, but many of these methods are prohibitive in industry due to high energy, material and labor requirements. This study investigated two emerging technologies to treat AMD with high removal rates of some metals. In addition, as AMD contains strategic metals such as rare earth elements (REEs), hydrometallurgical and biosorptive approaches were used to recover REEs from AMD, hydrometallurgical recovery method was also applied for coal by-products for the method developed. A two-chamber bioelectrochemical system (BES) was used to remove different types of metals from AMD. After 7 days, the pH of the cathode solution increased from 2.5 to 7.3. More than 99% of Al, Fe and Pb were removed, and removal rates of 93%, 91%, 89% and 69% were achieved for Cd, Zn, Mn, and Co, respectively, at the biocathode. Energy-dispersive X-ray spectroscopy (EDS) studies revealed the deposition of the various metals on the cathode surface, and some metals were detected in precipitates from the cathode chamber. During the BES operation, ~30-50 mV of closed circuit voltage was obtained for different conditions. A single-chambered BES study was conducted for the removal of Cd, Ni, and Mn in mine drainage. Compared to a double chamber, a single chamber BES is easier to design and operate. The removal process was studied with activated sludge from a local wastewater treatment plant. The effect of applied voltage, time, and initial concertation of these metals on their removal rate was studied. For Cd initial concentrations of 625 and 165 µg/L, 1.0 V showed the highest removal efficiency, and ~93 and 95% of Cd were removed, respectively. For a Ni initial concentration of 2,440 µg/L, 72% was removed under 1.0 V compared to the control of 77%. However, for a lower initial Ni concentration of 190 µg/L, 1.0 V was better compared than other conditions, and it removed 92% of Ni. For a Mn initial concentration of 1,800 µg/L, 1.0 V had a better result, however, only ~19% of the Mn was removed. For a lower Mn initial concentration of 390 µg/L, 1.0 V was favorable only at 24 h and the removal rate was ~37%. Nanoscale zerovalent iron (nZVI) was used to remove contaminants from AMD. These contaminants include transition metals (Co, Ni, Cu, Mn, and Zn), alkali and alkaline earth metals (Li, Mg, and Ca), metalloid (As), nonmetals (Se and S), and active metal (Al). Purchased nZVI in concentrations of 10-6500 mg/L was used for a reaction duration of up to 480 min. The pH of the AMD increased linearly with increasing concentrations of nZVI, with a maximum of 6.0±0.1 at 6500 mg/L of nZVI. Cu and Al had the highest removal rate among all other elements. With 10 mg/L of nZVI, ~100% of Cu was removed within 120 min. Up to ~98% of Al was removed with 5000 mg/L of nZVI in 480 min. Reuse of the purchased nZVI was studied for the first time for AMD treatment; however, after reuse in the second cycle, the nZVI was no longer effective. Lab-made nZVI by the precipitation method was tested for a longer time of 48 h. Removal rates for different elements did not change after ~8 h (e.g., 480 min), and in general, the lab-made nZVI had better removal efficiency compared to the purchased nZVI, with removal rate of ~28-79% when using 80 mg/L of the lab-made nZVI. Besides Cu, Al, Ni, and Co, successful removal of Mg and Ca, as well as S, Co, Li, As, and Se from AMD was reported for the first time by using nZVI. Different coal ranks were examined for REE concentration from coal ash. Maximum REE content of more than 700 mg/kg was observed for the highest-rank coal (anthracite) sample, and that was used for leaching and recovery studies. Hydrometallurgical processes including leaching, solvent extraction, stripping, and precipitation were performed to recover REEs from coal ash. Nitric acid leaching tests were conducted at 95 ℃ using a 4×2×2 factorial design. The results indicated that the highest rate of light REEs (LREEs) recovery was achieved at the highest molarity of the acid solution, lowest solids content and longest retention time. However, the highest rate of heavy REEs (HREEs) recovery needed only an intermediate level of acid molarity. The highest recovery rates of 90% for LREEs and 94% for HREEs were obtained. Recirculation of the leachate was conducted to prepare the REE-concentrated solution for the solvent extraction. After two stages of leaching, a 33 mg/L of TREE concentration was obtained in the leachate. Solvent extraction (SX) tests conducted using three different extractants, namely, TBP, D2EHPA and Cyanex 572, and their combinations showed that D2EHPA was the best extractant for recovering REEs from the nitric acid leachate solution with an extraction efficiency of 99%. Nitric acid and sulfuric acid and their mixture were used in the stripping tests. The effect of solvent concentration (in the SX process) was also studied in the stripping stage. When 50% solvent concentration was used, a maximum of 58% stripping recovery was obtained. Oxalic acid helped precipitate ~94% of total REEs (TREEs) from the above aqueous solution. Calcination of the product was performed to reach a final product of 0.8% rear earth oxides (REOs). The same process flowsheet was also successfully tested for another coal ash sample. To recover REEs from AMD, two different approaches were carried out including hydrometallurgical technique and more environmentally friendly approach- biosorptive recovery. A complete process flowsheet including either solvent extraction or biosorption, followed by stripping, and precipitation was developed to recover REEs from an unconventional source of AMD for the first time. At the natural pH of 2.5 almost all REEs were extracted from the solution. Metal-loaded organic solution was reused for three cycles, and it was shown that after three cycles, there was no major reduction in the capacity of the extractant. Striping with 6.0 M HNO3 recovered 23.9±0.7, 74.7±2.1, and 53.1±1.4% of LREEs, HREEs, and TREEs from the organic phase accordingly. Using oxalic acid, and for pH of 2.0, 92.9±2.8% of LREEs, 10±1.5% of HREEs, and 56.2±1.8% of TREEs were precipitated. In the biosorptive extraction, >99% of TREEs were extracted from the solution. The REE-bearing bacteria was also stripped with 6.0 M HNO3, 2871.3±114.8 µg/L (45.0±1.8%) LREEs, 3851.0±154.0 µg/L (65.0±2.6%) HREEs, and 6722.0±268.9 µg/L (50.0±2.0%) TREEs were obtained. Both hydrometallurgical and biosorptive methods extracted almost all of the REEs in the AMD, though pH was adjusted to 4.0 for the biosorptive method. After stripping, comparable amounts of TREEs were obtained by both methods.