Synergistic effects of biogenic manganese oxide and Mn(II)-oxidizing bacterium Pseudomonas putida strain MnB1 on the degradation of 17 α-ethinylestradiol.

While biogenic manganese oxide (BMO) generated via the oxidation of Mn(II) by the Mn-oxidizing bacteria (MOB) have received attention, the relative roles of biological activity by MOB themselves were not clearly investigated. In this study, the synergistic effects of BMO and MOB Pseudomonas putida strain MnB1 on the degradation of 17α-ethinylestradiol (EE2) was investigated. Experiments with BMO in the presence of P. putida MnB1 showed 15-fold higher removal than that with BMO alone, suggesting that EE2 degradation was mediated by the biological activity of MOB as well as abiotic reaction by BMO. Trapping experiments with pyrophosphate (PP) proved that Mn(III) intermediate formed during the biological process from Mn (II) to Mn (IV) contribute much to the EE2 removal. Also, sharp decreases in EE2 removal were observed when microbial activity was inactivated by heat treatment or sodium azide. From this study, the EE2 removal mechanisms by BMO in the presence P. putida MnB1 are described as follows: (1) abiotic oxidation of EE2 by BMO occurs. (2) P. putida MnB1 indirectly oxidizes EE2 by transferring electrons from the Mn (III) intermediate. (3) P. putida MnB1 continuously re-oxidizes the Mn(II) released from the oxidative degradation of EE2 by BMO, generating new Mn(III)-intermediates or BMO.