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No description available.

Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1992. / Vita. Abstract. Includes bibliographical references (leaves 130-136). Also available via the Internet.

Microconstituents (MCs) have become an emerging concern to scientists and researchers. Due to the development of analytical technology, it is now possible to study MCs at ηg/L to μg/L levels. Wastewater treatment plants (WWTPs) are the major point source for MCs entering the environment based on the literature. WWTPs are known to be unable to remove many MCs to a safe level. In order to fully understand the fate of MCs in WWTPs and to further improve the design of WWTPs in terms of MC removal, it is necessary to examine removal mechanisms such as sorption and biodegradation in WWTPs. Three MCs, bisphenol A (BPA), 17-α-ethinylestradiol (EE2) and triclosan (TCS), were chosen for this study. They are chemicals reported to be hydrophobic and have low vapor pressure, which makes sorption a highly potential removal mechanism. Primary sludge and activated sludge (AS) were used to perform sorption kinetics and isotherm experiments for BPA, EE2 and TCS. Primary sludge was collected from local WWTPs, and AS was generated from a lab-scale continuous flow bioreactor system maintained at solids retention times of 15, 10 and 5 d and hydraulic retention time (HRT) of 6 h. Alum was added to synthetic wastewater influent at concentrations typically used for phosphorus removal at some plants. Alum has the potential to change sludge structure and influence the sorption process. A comparison was made with AS as the adsorbent with and without alum addition to the AS to study the influence of alum on the sorption processes. The selected MCs were found to reach sorption equilibrium with primary sludge within 7 h. A pseudo second-order kinetic model was an excellent fit to describe the sorption processes of selected MCs. The solids-liquid partitioning coefficient (Kd) was determined for the three chosen MCs. The Kd values found for primary sludge and AS are very close. The Kd for MCs sorbed to AS in this study were compared with the Kd for AS without alum addition. Although alum addition showed no influence on effluent soluble chemical oxygen demand, it decreases the Kd for BPA and EE2 sorbed to AS. In contrast, a much higher Kd for TCS was observed for AS with alum addition. Judging from the R2 values, the linear sorption model is not suitable for some of the isotherms. Langmuir and Freundlich sorption isotherms were further used to fit the experimental data by applying linear regression and nonlinear regression approaches. The Freundlich isotherm was found to be the most suitable model to describe the experiment data.

Effects of several important source-related and operation-related factors on particle formation and growth as well as potential particle and dissolved organic matter removal by alum coagulation are described. Two representative natural water sources, with low turbidities and high concentrations of dissolved organic matter, and one commercially available crystalline silica, with defined characteristics, were employed to establish initial aquatic particle and dissolved organic matter conditions. Six experimental variables utilized for evaluation include initial pH, initial turbidity, applied pre-ozonation dose, alum dose, flocculation time and sedimentation time. A bench-scale experimental apparatus with capabilities of ozonation, coagulation, sedimentation and membrane filtration was employed to conduct a series of selected experiments. Each factor investigated in this research proves to be able to inpart, individually or collectively, statistically significant effects on particle formation and growth during alum coagulation. While the addition of model particles shows significant enhancement in particle growth, it fails to demonstrate significant improvement in the removal of dissolved organic matter. On the contrary, effects of pH and alum dose on particle formation and growth are accompanied by corresponding effects on the removal of dissolved organic matter. Pre-ozonation of dissolved organic matter renders the dissolved organic matter more hydrophilic by increasing the number of carboxylic acid functional groups. This phenomenon can significantly improve or impede particle growth as well as dissolved organic matter removal during alum coagulation, depending on raw water chemistry and other operational factors. Alum coagulation under all of the conditions investigated in this research is demonstrably more effective in removing aquatic humic susbtances with higher apparent molecular weights and fewer carboxylic acid functional groups, as opposed to those with lower apparent molecular weight and more carboxylic acid functional groups. The predominant removal mechanisms were found to occur at the beginning stage of the coagulation process; that is, the rapid mixing period. The remaining dissolved organic matter and humic substances can form significant amounts of trihalomethanes upon reaction with chlorine.

Hydrous aluminum oxide colloids of 0.5 Am diameter were used to study the coagulation of submicron particles under water-treatment conditions. The research was aimed at understanding the effects of pH and ligands (organic and inorganic) on precipitation of the added coagulant and their influences on incorporation of the colloids into larger flocs. The reduction in the concentration of submicron particles as a result of alum coagulation was monitored by conventional jar-test experiments. Scanning electron microscopy was used for submicron particle counting. Up to three orders of magnitude reduction in submicron particle concentrations were observed in jar-test experiments. Higher pH (i.e., 7.5) and alum dose (i.e., 1.0 mg L⁻¹) favored homogeneous precipitation of aluminum hydroxide, whereas heterogeneous precipitation occurred at lower pH (i.e., 6.5) and alum dose (i.e., 0.5 mg L⁻¹). Homogeneous precipitation, involving formation of Al(OH)₃(s) from aqueous species, formed large masses of light-weight flocs that can effectively remove submicron particles by subsequent coagulation. Heterogeneous precipitation, which involves precipitation on the surfaces of the seed particles, resulted in destabilized particles that can efficiently coagulate with each other. The presence of ligands, inorganic (e.g., HCO₃⁻) and organic (e.g., functional groups of humic substances) inhibited the coagulation process, reducing particle removal up-to 250 fold. While these ligands inhibit coagulation by modifying particle surfaces, they may enhance the precipitation reactions of aluminum hydroxide. The presence SO₄²⁻ enhanced precipitation relative to NO₃⁻. Electrophoretic mobility values were used to derive equilibrium constants for aluminum speciation and precipitation reactions, both on the surface of particles and in solution. The adsorption of ligands lowered the pHiep, by almost 2 pH units in the presence of HCO₃⁻, and to a pH of less than 3 in the presence of organics. Aluminum species elevated the pHiep by 1 pH unit. Stoichiometric ratios of aluminum hydroxide precipitation were determined using a pH stat. This ratio (1.9 to 3.7) is a function of pH, and concentrations of particles and organics. These results were modeled as spherical precipitates (OH/A1 =3) with adsorbed aluminum species (OH/A1 = 1 to 4). The results of this research suggest that the aluminum precipitation pathway dictates the removal of submicron particles. Submicron particles provide most of the surfaces from particulate matter, thus suggesting the importance of surface precipitation for their removal. Samples from water treatment plants indicated 1.5 to 2.0 log removal of submicron particles. These plants were operating at higher pH values (above 7.5) relative to that of maximum removal experiments in laboratory. Plant operations can be optimized by careful control parameters affecting supersaturation ratio, thus improving removal of submicron particles.Such optimization should include efficient rapid mixing to achieve uniform upersaturation ratios, proper coagulant dose, and possibly better pH control.

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Some community water systems using sources containing elevated levels of fluoride, in the United States and worldwide, struggle to treat their drinking water to healthy fluoride concentrations. Many treatment plants in the U.S. currently use aluminum based salts, such as aluminum sulfate and polyaluminium chloride, as coagulants during conventional treatment for removal of particles from drinking water sources. Moreover, enhanced aluminum sulfate, or alum, coagulation requires higher concentrations of aluminum added to the process and has been shown to be effective for removal of disinfectant byproduct precursors, i.e., natural organic matter (NOM). The presence of fluoride may interfere with the formation of aluminum hydroxide precipitates, and interrelationships among NOM, aluminum precipitation and fluoride removal are not well understood. A fundamental understanding of how fluoride alters the properties of aluminum precipitates and how fluoride and NOM molecules compete as ligands interacting with soluble aluminum species is lacking. As a result, the development of guidelines for implementation and optimization of a treatment scheme that uses aluminum in the presence of fluoride requires a multi-faceted approach in which the development of a mechanistic understanding of these interactions is conducted in concert with macroscopic experiments to identify optimum conditions for simultaneous removal of fluoride and NOM. To date, little research has looked at the efficiency of removing both fluoride and organics from the perspective of the precipitation process. To provide a foundation for revising treatment techniques, this research evaluated the effect of co-precipitating aluminum in the presence of fluoride, organics, and in multi-ligand systems to characterize the solid precipitate and removal competition. This research verified the formation of a co-precipitate in the presence of fluoride and certain low molecular weight organics. Co-precipitation from organics and fluoride competes for removal, especially at low alum coagulant doses, complicating treatment for resource limited areas. / text

Thesis (M.S.)--University of Delaware, 2005. / Principal faculty advisor: Donald L. Sparks, Dept. of Plant & Soil Sciences. Includes bibliographical references.

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