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Evaluation of prior research and preliminary investigations in our laboratory led to the development of an extraction strategy that can be used to target different cations in activated sludge floc and extract their associated extracellular polymeric substances (EPS). The methods we used were the cation exchange resin (CER) procedure, base extraction, and sulfide addition to extract EPS linked with divalent cations, Al, and Fe, respectively. A comparison of sludge cations before and after CER extraction revealed that most of Ca(2+) and Mg(2+) were removed while Fe and Al remained intact, suggesting that this method is highly selective for Ca(2+) and Mg(2+)-bound EPS. The correlation between sludge Fe and sulfide-extracted EPS was indicative of selectivity of this method for Fe-bound EPS. The base extraction was less specific than the other methods but it was the method releasing the largest amount of Al into the extract, indicating that the method extracted Al-bound EPS. Concomitantly, the composition of extracted EPS and the amino acid composition differed for the three methods, indicating that EPS associated with different metals were not the same. The change in EPS following anaerobic and aerobic digestion was also characterized by the three extraction methods. CER-extracted EPS were reduced after aerobic digestion while they changed little by anaerobic digestion. On the other hand, anaerobic digestion was associated with the decrease in sulfide-extracted EPS. These results suggest that different types of cation-EPS binding mechanisms exist in activated sludge and that each cation-associated EPS fraction imparts unique digestion characteristics to activated sludge.

Autothermal thermophilic aerobic digestion of sludge is known to produce poorly dewatering sludges. Laboratory studies were conducted to investigate the reasons for the poor dewatering. It was found that, during digestion, proteins and polysaccharides were released into solution, and that these could be linked to the deterioration in dewatering. The biopolymer release was accompanied by an increase in the monovalent-to-divalent (M/D) cation ratio. The degree to which the M/D caused deterioration of the sludges depended on the presence of iron in sludge. When the iron content was high, the release of protein and polysaccharides was low. When iron was low, the release of protein and polysaccharides increased linearly with the M/D ratio. The dose of conditioning chemicals, cationic polymer or ferric chloride, was related to the amount of colloidal biopolymer present in solution. The findings suggest that the addition of iron during the digestion process has the potential to produce better dewatering sludges.

With all the advances made in understanding the structure and composition of sewage sludges, chemical conditioning remains a trial and error process, both with regard to the type and dose of conditioner needed. Recent studies at Virginia Tech have found that biological floc consists of two types of biopolymer, material associated with iron and aluminium and material associated with calcium and magnesium. These materials behave differently when sludges undergo digestion. This results in very different material being released into solution during digestion and very different conditioning requirements. This study shows that the primary materials released during anaerobic digestion are proteins and coagulation of the colloidal protein fraction in solution is the primary mechanism for conditioning. For aerobically digested sludges, both proteins and polysaccharides make up the colloid fraction, which interferes with dewatering. This research also shows that the effectiveness of the digestion process as characterized by volatile solids destruction is directly related to the chemical dose required for conditioning. That is, as the solids destruction increases, the conditioning chemical requirement also increases. Well digested sludges dewater more poorly and require more conditioning chemical than those with less volatile solids destruction.

Laboratory anaerobic and aerobic digestion studies were conducted using waste activated sludges from two municipal wastewater treatment plants in order to gain insight into the mechanisms of floc destruction that account for changes in sludge conditioning and dewatering properties when sludges undergo anaerobic and aerobic digestion. Batch digestion studies were conducted at 20 degrees C and the dewatering properties, solution biopolymer concentration and conditioning dose requirements measured. The data indicated that release of biopolymer from sludges occurred under both anaerobic and aerobic conditions but that the release was much greater under anaerobic conditions. In particular, the release of protein into solution was 4-5 times higher under anaerobic than under aerobic conditions. Both the dewatering rate, as characterized by the specific resistance to filtration and the amount of polymer conditioning chemicals required was found to depend directly on the amount of biopolymer (protein + polysaccharide) in solution. Little difference in dewatering properties and conditioning doses was seen between the two activated sludges from different plants. Differences in the cations released between anaerobic and aerobic digestion suggest that the digestion mechanisms differ for the two types of processes. Enzyme activity data showed that during aerobic digestion, polysaccharide degradation activity decreased to near zero and this was consistent with the accumulation of polysaccharides in aerobic digesters.

Laboratory experiments and field tests were conducted to determine the effect of inorganic cations on effluent from activated-sludge systems. Laboratory experiments showed that monovalent cations tend to increase the concentration of solution biological polymers (biopolymers), whereas divalent cations tend to retain the biopolymers in the floc. Biopolymers in solution affect effluent chemical oxygen demand (COD). Coagulation tests were performed on the effluent with ferric chloride. Ferric hydroxide can coagulate protein through possible adsorptive interactions and may be responsible for some biopolymer retention in the flocs. In the field study, it was found that sodium ions in the influent wastewater caused an increase in proteins and polysaccharides in solution, thereby increasing the effluent COD concentration of the treated municipal wastewater. The attachment or release of these microbially derived organic biopolymers and recalcitrant influent substrate may depend on the monovalent-to-divalent cation ratio and the concentration of iron. Modeling of effluent organics in the activated-sludge process can be enhanced through incorporation of concepts that take into account the partitioning (between floc and solution) of microbial biopolymers and influent recalcitrant substrate.