Reyes Sierra-Alvarez, Victor M. Gamez, and Jim A. Field. University of Arizona, Tucson, AZ
This study examined the feasibility of an innovative system configuration that combines a crystallization reactor and a sulfate-reducing anaerobic bioreactor for the simultaneous removal of heavy metals and organic contaminants. Metal removal is stimulated by biogenic sulfides produced by immobilized sulfate reducing bacteria in a high-rate anaerobic bioreactor. Heavy metals are then deposited in sand granules inside a separate fluidized bed containing fine sand (crystallization reactor). The sand offers surfaces for the nucleation of metal sulfides and subsequent crystal growth. Metal sulfides can then be recovered from the sand granules in a purified form. A 3 L-bioreactor coupled to a 0.40 L-crystallization reactor was fed a synthetic semiconductor wastewater. The bioreactor was operated under non-limiting sulfate conditions at a hydraulic retention time of 8 h. The simulated influent contained sulfate, divalent copper (60-100 mg/L), and citric acid at a concentration of 660 or 2000 mg chemical oxygen demand (COD)/L, depending on the experimental period. Soluble and total copper were successfully removed in the bioreactor-crystallization reactor system (over 99.0% elimination). Copper precipitated selectively in the crystallization reactor (> 99.0% removal of soluble Cu); however, removal of total copper by the crystallizer was less efficient (80.7-100%), suggesting that a fraction of the metal-sulfide minerals precipitated in the bulk media. Analysis by SEM-EDS and XR diffraction confirmed extensive precipitation of copper minerals (covellite, CuS) on the sand surface. Organic removal efficiencies above 90% were achieved by the system in spite of the high concentrations of toxic metals present in the influent. These results indicate that metal biomineralization by biogenic sulfides and separation of the formed sulfide minerals in a crystallization reactor is a promising approach for the removal of copper and other heavy metals in contaminated effluents. Simultaneous removal of oxygen-demanding organic contaminants is an additional benefit of the proposed treatment system.
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