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Synthesis and characterisation of low-cost biopolymeric/mineral composite systems and evaluation of their potential application for heavy metal removal

Heavy metal pollution and waste management are two major environmental problems faced in the world today. Anthropogenic sources of heavy metals, especially effluent from industries, are serious environmental and health concerns by polluting surface and ground waters. Similarly, on a global scale, thousands of tonnes of industrial and agricultural waste are discarded into the environment annually. There are several conventional methods to treat industrial effluents, including reverse osmosis, oxidation, filtration, flotation, chemical precipitation, ion exchange resins and adsorption. Among them, adsorption and ion exchange are known to be effective mechanisms for removing heavy metal pollution, especially if low-cost materials can be used. This thesis was a study into materials that can be used to remove heavy metals from water using low-cost feedstock materials. The synthesis of low-cost composite matrices from agricultural and industrial by-products and low-cost organic and mineral sources was carried out. The feedstock materials being considered include chitosan (generated from industrial seafood waste), coir fibre (an agricultural by-product), spent coffee grounds (a by-product from coffee machines), hydroxyapatite (from bovine bone), and naturally sourced aluminosilicate minerals such as zeolite. The novel composite adsorbents were prepared using commercially sourced HAp and bovine sourced HAp, with two types of adsorbents being synthesized, including two- and three-component composites. Standard synthetic methods such as precipitation were developed to synthesize these materials, followed by characterization of their structural, physical, and chemical properties (by using FTIR, TGA, SEM, EDX and XRD). The synthesized materials were then evaluated for their ability to remove metal ions from solutions of heavy metals using single-metal ion type and two-metal ion type solution systems, using the model ion solutions, with quantification of their removal efficiency. It was followed by experimentation using the synthesized adsorbents for metal ion removal in complex systems such as an industrial input stream solution system obtained from a local timber treatment company. Two-component composites were considered as control composites to compare the removal efficiency of the three-component composites against. The heavy metal removal experiments were conducted under a range of experimental conditions (e.g., pH, sorbent dose, initial metal ion concentration, time of contact). Of the four metal ion systems considered in this study (Cd²⁺, Pb²⁺, Cu²⁺ and Cr as chromate ions), Pb²⁺ ion removal by the composites was found to be the highest in single-metal and two-metal ion type solution systems, while chromate ion removal was found to be the lowest. The bovine bone-based hydroxyapatite (bHAp) composites were more efficient at removing the metal cations than composites formed from a commercially sourced hydroxyapatite (cHAp). In industrial input stream solution systems (containing Cu, Cr and As), the Cu²⁺ ion removal was the highest, which aligned with the observations recorded in the single and two-metal ion type solution systems. Arsenate ion was removed to a higher extent than chromate ion using the three-component composites, while the removal of chromate ion was found to be higher than arsenate ion when using the two-component composites (i.e., the control system). The project also aimed to elucidate the removal mechanisms of these synthesized composite materials by using appropriate adsorption and kinetic models. The adsorption of metal ions exhibited a range of adsorption behaviours as both the models (Langmuir and Freundlich) were found to fit most of the data recorded in different adsorption systems studied. The pseudo-second-order model was found to be the best fitted to describe the kinetics of heavy metal ion adsorption in all the composite adsorbent systems studied, in single-metal ion type and two-metal ion type solution systems. The ion-exchange mechanism was considered as one of the dominant mechanisms for the removal of cations (in single-metal and two-metal ion type solution systems) and arsenate ions (in industrial input stream solution systems) along with other adsorption mechanisms. In contrast, electrostatic attractions were considered to be the dominant mechanism of removal for chromate ions.
Type of thesis
The University of Waikato
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