The copper refinery process produces Se(VI)-bearing wastewater with a high content of Cl<sup>−</sup> and SO<sub>4</sub><sup>2−</sup> ions. To overcome the negative effect caused by Cl<sup>−</sup> and SO<sub>4</sub><sup>2−</sup> ions on Se(VI) reduction and its following removal, this study investigated the possible synergistic effect of the combination of Se(VI)-reducing bacterium, <i>Thaurea</i> (<i>T.</i>) <i>selenatis</i> and zero-valent iron (ZVI). In the presence of SO<sub>4</sub><sup>2−</sup> (200 mM) and Cl<sup>−</sup> (300 mM), the following was observed: (i) ZVI alone was unable to remove Se both under strictly aerobic and micro-aerobic conditions. (ii) Se(VI) reduction by <i>T. selenatis</i> alone was severely inhibited under anaerobic conditions (and thus no microbial growth was observed). (iii) On the other hand, <i>T. selenatis</i> was capable of growth and Se(VI) reduction under micro-aerobic conditions. (iv) Combining <i>T. selenatis</i> and ZVI under micro-aerobic conditions showed a synergistic effect on Se(VI) reduction, readily facilitating Se removal. This synergistic effect was optimized by adjusting the pH to near neutral (optimal for <i>T. selenatis</i> growth), but by adjusting the temperature to 35°C (sub-optimal for <i>T. selenatis</i> growth): Se removal of 55% by <i>T. selenatis</i> alone, was significantly improved to 98% by combining <i>T. selenatis</i> and ZVI. The proposed key process to display the synergistic effect on Se removal under micro-aerobic conditions is as follows: (i) Using the remaining dissolved O<sub>2</sub> (DO) during the first hours, <i>T. selenatis</i> can overcome the inhibitory effect of Cl<sup>−</sup> and SO<sub>4</sub><sup>2−</sup> by growing with more energy-gaining aerobic respiration, (ii) ZVI indirectly serves as a reducing agent to maintain low DO levels, consequently readily switching from aerobic to anaerobic Se(VI) respiration by <i>T. selenatis</i>. (iii) ZVI may also be acting directly for Se deposition by reducing microbially-produced intermediate Se(IV), which is more reactive than original Se(VI). The present findings could be used as a basis for developing an economically feasible and environmentally harmless bio-treatment technology for Se(VI) containing copper refinery wastewaters.
Okibe, N., Sueishi, K., Koga, M., Masaki, Y., Hirajima, T., Sasaki, K., ... Asano, S. (2015). Selenium (Se) Removal from Copper Refinery Wastewater Using a Combination of Zero-Valent Iron (ZVI) and Se(VI)-Reducing Bacterium, <i>Thaurea selenatis</i> Materials Transactions, 56(6), 889-894. https://doi.org/10.2320/matertrans.M2014457