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Studies were conducted to determine the role of bioflocculation in the activated sludge unit processes. Laboratory and full-scale studies revealed that bioflocculation is important in determining settling, dewatering, effluent and digested sludge properties (activated sludge properties) and may be vital to the function of all processes related to the above properties. In these studies, it was shown that divalent cations such as calcium and magnesium improved activated sludge properties, whereas monovalent cations such as sodium, potassium and ammonium ions were detrimental to these properties. The divalent cations promoted bioflocculation through charge bridging mechanisms with negatively charged biopolymers (mainly protein and polysaccharide). It was found that oxidized iron plays a major role in bioflocculation and determination of activated sludge properties through surface interactions between iron and biopolymers. Oxidized iron was effective in removing colloidal biopolymers from solution in coagulation and conditioning studies. The research included experiments evaluating effects of potassium and ammonium ions on settling and dewatering properties; effects of magnesium on settling properties; effects of sodium, potassium, calcium and magnesium on effluent quality; effect of solids retention time on effluent quality; and evaluation of floc properties during aerobic and thermophilic digestion. A floc model is proposed in which calcium, magnesium and iron are important to bioflocculation and the functionality of aeration tanks, settling tanks, dewatering equipment and aerobic or anaerobic digesters. It is shown that activated sludge floc properties affect wastewater treatment efficiency. / Ph. D.

An activated sludge system that incorporates a sidestream anaerobic bioreactor, called the Cannibal process, was the focus of this study. A prior study of this process (Novak et al., 2007) found that this system generated about 60% less solids than conventional activated sludge without any negative effects on the effluent quality. Although that study showed substantial solids reduction, questions remain concerning the specific mechanism(s) that account for the solids loss. In this study, the mechanisms that account for the loss of biological solids was the focus of the investigation. The first part of this study was conducted to evaluate those effects in terms of the role of iron in the influent wastewater and feeding patterns on the performance of the Cannibal system. It was found that the Cannibal system with high iron in the influent produced less biological solids than the system receiving low iron. The data also showed that the Cannibal system operated under fast feed (high substrate pressure) produced much less solids than the system with slow feed (low substrate pressure). The high substrate pressure was achieved by feeding the influent wastewater to the Cannibal system over a short time period so that the substrate concentration would initially peak and then decline as degradation occurred. This is called "fast feed." For low substrate pressure, the influent was added slowly so the substrate concentration remained low at all times. This is called "slow feed." Later, an attempt to increase substrate pressure in the slow feed Cannibal system was conducted by either manipulating the aeration patterns or adding a small reactor in front of the main reactor (selector). It was found that either interrupting aeration in the aerobic reactor or providing a small aerobic reactor in front of the main reactor resulted in an increase in solids reduction. The second part of this study was to investigate the mechanisms of floc destruction in the fast and the slow feed Cannnibal systems. It was found that higher accumulation of biopolymers (proteins and polysaccharides) occurred in the fast feed system and this was associated with a greater solids reduction in the fast than the slow feed system. In addition, more protein hydrolysis and more Fe(III)-reducing microorganism activity in the fast feed environment were found to be factors in higher solids reduction. The last part of this study was to investigate the structure of the Cannibal sludge flocs generated under the fast and the slow feed conditions. It was found that the readily biodegradable (1 kDa.) protein is larger in the flocs from the fast feed than the slow feed Cannibal system. This resulted in higher floc destruction in the fast feed condition. / Ph. D.

Throughout the study of polymer adsorption at the air/water and solid/water interfaces, surface tension measurements and surface plasmon resonance (SPR) spectroscopy have been identified as key methods for the acquisition of structural and thermodynamic information. These techniques were used to determine air/water and cellulose/water interfacial properties of pullulan (P) and pullulan cinnamates (PCs), 2-hydroxypropyltrimethylammonium xylans (HPMAXs), and hydroxypropyl xylans (HPXs). Hydrophobic modification of pullulan with cinnamate groups promoted adsorption onto model surfaces of regenerated cellulose. In order to understand the relative contributions of hydrophilic and hydrophobic interactions towards PC adsorption, PC adsorption onto self-assembled monolayers (SAMs) with different functional groups was also studied. As the degree of cinnamate substitution increased, greater adsorption onto cellulose, methyl-terminated SAMs (SAM-CH3), and hydroxyl-terminated SAMs (SAM-OH) was observed. This study showed that hydrogen bonding alone could not provide a complete explanation for PC adsorption onto cellulose. The adsorption of cationic 2-hydroxypropyltrimethylammonium (HPMA) xylans with different degrees of substitution (DS) onto SAMs and regenerated cellulose was studied by SPR. Surface concentration (Р) exhibited a maximum (Рmax) for HPMAX adsorption onto carboxylic acid-terminated SAMs (SAM-COOH) at an intermediate HPMA DS of 0.10. This observation was indicative of a relatively flat conformation for adsorbed HPMAXs with higher HPMA DS because of higher linear charge densities along the polymer backbone. Рobserved for HPMAX adsorption onto regenerated cellulose and SAM-OH surfaces was relatively low compared to HPMAX adsorption onto SAM-COOH surfaces. Surface tension measurements for aqueous solutions of HPX by the Wilhelmy plate technique showed that surface tension changes ("γ = γwater " γHPX(aq)) increased and critical aggregation concentrations generally decreased with increasing hydroxypropyl (HP) DS. Hence, even though HP substitution was necessary to induce aqueous solubility, excessive hydroxypropylation promoted aggregation in water. SPR studies indicated that HPXs did not adsorb significantly onto regenerated cellulose or SAM-OH surfaces (submonolayer coverage). In contrast, HPX did adsorb (~monolayer coverage) onto SAM-CH3 surfaces. Collectively, these studies showed natural polymers could be chemically modified to produce surface modifying agents with sufficient chemical control, whereby the surface properties of the resulting systems could be explained in terms of chemical structure and intermolecular interactions. / Ph. D.