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.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24100号 / 工博第5022号 / 新制||工||1748(附属図書館) / 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 清水 芳久, 教授 松井 康人 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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Heavy metals, despite their essential roles as minerals in biological systems, pose a significant threat to human health and the environment due to their toxic properties. Even at low concentrations, heavy metals such as lead, mercury, arsenic, and cadmium can cause adverse effects on humans and animals. Consequently, stringent regulations have been established to limit heavy metal concentrations in water resources. However, existing laboratory-based analytical methods for heavy metal detection are time-consuming, expensive, and require skilled personnel. The current detection limit required by several health organizations around the globe is below 10 ppb for Lead, Mercury, Chromium, and Arsenic. The current state of the art which can accomplish low levels of detection is either expensive to operate or incapable of achieving the required trace level sensing. This thesis aims to address the need for a simple, cost-effective, and portable method for detecting heavy metals in water. The thesis begins by reviewing the current state-of-the-art heavy metal sensing methods, highlighting their limitations and the requirement for sample preconcentration. Various preconcentration techniques are discussed, emphasizing their performance parameters and advancements in trace-level detection. Furthermore, the thesis identifies the gaps in current technology, particularly in the context of developing a reliable and user-friendly method for testing heavy metal concentrations in drinking and surface waters. The primary objective of this thesis is to develop a preconcentration-based colorimetric method for detecting heavy metals in water. This method aims to overcome the limitations of existing techniques by offering high sensitivity and a limit of detection below regulatory ranges without the need for complex equipment or extensive sample preparation. The thesis contributes to the advancement of the state-of-the-art by providing a simplified, portable, and efficient solution for in-line detection of heavy metal contamination in water resources. This has been achieved through the design and deployment of sensor utilizing a novel architecture, measuring heavy metal ions down to the sub ppb level. we were able to detect ions such as copper and Lead at concentrations below 0.5 ppb with a limit of detection (LOD) of 0.14 ppb. Overall, this thesis combines knowledge from the fields of analytical chemistry, sensor technology, and environmental science to address the pressing need for a practical and accessible method for monitoring heavy metal concentrations in water. By achieving this goal, the research will contribute to safeguarding public health and promoting sustainable water resource management. / Thesis / Doctor of Philosophy (PhD) / Heavy metals can be found naturally and are needed in small amounts for our bodies to function properly. However, many heavy metals are toxic and can cause serious health problems even at very low concentrations. These metals can contaminate water sources through activities like mining and improper waste disposal. Currently, detecting heavy metals in water requires expensive equipment and skilled experts in a laboratory setting. This process is time-consuming and not easily portable for on-site testing. The existing methods also have limitations such as low sensitivity or the need for complex procedures. This thesis aims to improve the way we detect harmful heavy metals in water. The goal of this thesis is to develop a simpler and more sensitive method for detecting heavy metals in water. The focus is on using color-changing dyes that react to the presence of heavy metal ions. However, these dyes often have detection limits higher than what is considered safe, so the thesis also explores ways to concentrate the samples to improve sensitivity. By addressing these challenges, the thesis aims to contribute to the development of a reliable and easy-to-use method for testing heavy metal concentrations in drinking and surface waters, helping to protect public health and identify potential sources of contamination.

An increasingly recognized problem in the world is stormwater runoff and its generation of pollutants in urban areas. Stormwater treatment technologies have therefore increased in implementation to prevent this pollution. One of these preventions are detention ponds, which primary function is the equilibration of water, but have also proven to have the capacity to remove many particle-bound pollutants by sedimentation. What's not as known is to what extent. The investigated detention ponds were compared to see to what extent they had accumulated particle-bound elements such as heavy metals, phosphorus and sulphur. This because it is essential to clarify whether they embody ecotoxicological hotspots and if when dredged will have sediment classified as hazardous waste. What was found in this study was that there was no significant difference in accumulation of pollutants or sediment depending on inlet or outlet, a difference between these could still be seen though by looking at the figures. The sediment of some of the detention ponds also had levels of the investigated elements higher than existing guideline values recommend for living organisms in the sediment and could also be classified as hazardous waste when emptied. More investigations need to be done, for example about how hydrology, plant uptake and design affect the sedimentation of pollutants to know for sure how the accumulation of pollutants in detention ponds work.

Increasing population across the globe paved the way for rapid growth in industrialization. Pharmaceuticals, automotive, textiles, agriculture, electronics, electrical and many other industries discharge different types of heavy metals, dyes and organic contaminants into ground water. These discharges are released into lakes and rivers without prior treatment causing huge environmental impact to the environment. Among different remediation techniques, adsorption was considered the most promising method because of its low-cost and high efficiency. Biomass is considered as the most practical and renewable source for production of bio products and biofuels. Biomass is also used for carbon sequestration and as an essential element to produce hydrochar and biochar which are considered as the 21st century black gold. Hydrochar and biochar can be used as an excellent low-cost adsorbent for the removal of heavy metals, dyes and organic contaminants from water. This dissertation work focuses on, firstly, development of novel oxone treated hydrochar as an adsorbent for the efficient removal of Pb(II) and Methylene Blue (MB) from aqueous solutions. Secondly, preparing novel ozone oxidized hydrochar treated with polyethyleneimine for removal of Remzol Brilliant Blue (RBB) and Remzol Reactive Black (RRB) dyes from aqueous solutions. Thirdly, producing high-performance CO2 activated biochar as an adsorbent for efficient removal of Aniline from aqueous solution. All prepared hydrochar and biochar adsorbents were characterized by SEM, TGA, FTIR, Elemental analysis, conductometric titration, and N2 adsorption-desorption isothermal analyses (BET and BJH). The adsorption capacities were determined by Atomic absorption spectrometry (AAS) and Ultraviolet–visible spectroscopy (UV-VIS) respectively. The adsorption capacity of each prepared biochar or hydrochar was determined and both kinetic and isothermal studies were performed. The optimal preparation conditions and adsorption parameters were determined for each adsorbent.