The investigation of photocatalysts and iron based materials in the oxidation and adsorption of toxic organic and chromium materials

The presences of heavy metals, organic contaminants and natural toxins in natural water bodies pose a serious threat to the environment and the health of living organisms. Therefore, there is a critical need to identify sustainable and environmentally friendly water treatment processes. In this dissertation, I focus on the fundamental studies of advanced oxidation processes and magnetic nano-materials as promising new technologies for water treatments. Advanced oxidation processes employ reactive oxygen species (ROS) which can lead to the mineralization of a number of pollutants and toxins. The rates of formation, steady-state concentrations, and kinetic parameters of hydroxyl radical and singlet oxygen produced by various TiO2 photocatalysts under UV or visible irradiations were measured using selective chemical probes. Hydroxyl radical is the dominant ROS, and its generation is dependent on experimental conditions. The optimal condition for generation of hydroxyl radical by of TiO2 coated glass microspheres is studied by response surface methodology, and the optimal conditions are applied for the degradation of dimethyl phthalate. Singlet oxygen (1O2) also plays an important role for advanced processes, so the degradation of microcystin-LR by rose bengal, an 1O2 sensitizer was studied. The measured bimolecular reaction rate constant between MC-LR and 1O2 is ∼ 106 M-1 s-1 based on competition kinetics with furfuryl alcohol. The typical adsorbent needs separation after the treatment, while magnetic iron oxides can be easily removed by a magnetic field. Maghemite and humic acid coated magnetite (HA-Fe3O4) were synthesized, characterized and applied for chromium(VI) removal. The adsorption of chromium(VI) by maghemite and HA-Fe3O4 follow a pseudo-second-order kinetic process. The adsorption of chromium(VI) by maghemite is accurately modeled using adsorption isotherms, and solution pH and presence of humic acid influence adsorption. Humic acid coated magnetite can adsorb and reduce chromium(VI) to non-toxic chromium (III), and the reaction is not highly dependent on solution pH. The functional groups associated with humic acid act as ligands lead to the Cr(III) complex via a coupled reduction-complexation mechanism. Extended X-ray absorption fine structure spectroscopy demonstrates the Cr(III) in the Cr-loaded HA-Fe 3O4 materials has six neighboring oxygen atoms in an octahedral geometry with average bond lengths of 1.98 Å.

Characterization of design and economic sensitivity of vapor phase carbon adsorption systems to environmental uncertainties

Vapor phase carbon adsorption systems are used to remove aromatics, aliphatics, and halogenated hydrocarbons. The adsorption capacity of granular activated carbon is reduced when environmental parameters (temperature, pressure, and humidity) interfere with homogeneous surface diffusion and pore distribution dynamics. The purpose of this study was to investigate the effects of parametric uncertainties in adsorption efficiency. ^ Modified versions of the Langmuir isotherm in conjunction with thermodynamic equations described gaseous adsorption of single component influent onto microporous media. Experimental test results derived from Wang et al. (1999) simulated adsorption kinetics while the Myer and monsoon Langmuir constant accounted for isothermal gas compression and energetic heterogeneity under thermodynamic equilibrium conditions. Responsiveness of adsorption capacity to environmental uncertainties was analyzed by statistical sensitivity and modeled by breakthrough curves. Results indicated that extensive fluctuations in adsorption capacity significantly reduced carbon consumption while isothermal variations had a pronounced effect on saturation capacity. ^

Adsorption and desorption of phosphate on limestone in experiments simulating seawater intrusion

This study investigates the potential release of from carbonate aquifers exposed to seawater intrusion. Adsorption and desorption of in the presence of deionized water (DIW) and seawater were conducted on a large block of Pleistocene age limestone to simulate the effects of seawater intrusion into a coastal carbonate aquifer at the laboratory scale. The limestone showed strong adsorption of in DIW, while adsorption was significantly less in the presence of seawater. Dissolution of CaCO3 was found to prevent adsorption at salinities less than 30 psu. Adsorption of was limited at higher salinities (30–33 psu), due to competition with ions for adsorption sites. At a salinity3 precipitated. Concentrations of between 2 and 5 μmol/L were released by desorption when the limestone was exposed to seawater. The results of this study suggest that as seawater intrudes into an originally freshwater coastal aquifer, adsorbed may be released into the groundwater. Consequently, adsorbed is expected to be released from coastal carbonate aquifers world-wide as sea level continues to rise exposing more of the freshwater aquifer to seawater.

AFM and SPR studies of protein adsorption at solid/liquid interface

Membrane-like structure formed by surfactant molecules of didodecyldimethylammonium bromide (DDAB) on both HOPG and gold electrodes were studied with AFM and SPR techniques. The study shows that the thickness of the adsorbed layer of DDAB is strongly dependent on the concentration of the vesicle solution. We have also investigated the adsorption of redox protein, Cytochrome c, on graphite electrode with in situ tapping mode AFM. The protein adsorbs spontaneously onto the electrode covered with an adsorbed phosphate layer and forms a uniform monolayer. The adsorbed protein exhibits a reversible electron transfer at 0.17 V (Ag/AgCI) once the electrode potential has been increased to 0.75V. Using surface plasmon resonance spectroscopy we have measured subtle conformational change in protein, Cyt c, due to electron transfer of a single electron on MPA-coated gold electrode. The electron transfer induced change in the resonant angle is about 0.006 deg., which corresponds to ~ 0.2 A decreases in the thickness. This is consistent with that reduced state is more compact than the oxidized state.