Enhanced triclosan and nutrient removal performance in vertical up-flow constructed wetlands with manganese oxides

Limited concentrations of oxygen in constructed wetlands (CWs) have inhibited their ability to remove emerging organic contaminants (EOCs) at μg/L or ng/L levels. Manganese (Mn) oxides were proposed as a solution, as they are powerful oxidants with strong adsorptive capabilities. In the present study, triclosan (TCS) was selected as a typical EOC, and CW microcosms with Mn oxides (birnessite) coated sand (B-CWs) and without (C-CWs) were developed to test the removal capacities of TCS and common nutrients. We found that the addition of Mn oxides coated sand significantly improved removal efficiencies of TCS, NH₄-N, COD, NO₃-N and TP (P < 0.05). The average concentration of Mn(II) effluent was 0.036 mg L^-1, mostly lower than the drinking water limit. To gain insight into the mechanisms of pollution removal, Mn transformation, dissolved oxygen (DO) distribution, bacterial abundance, and microbial community composition were also investigated. Maximum Mn(II) was detected at 20 cm height of the B-CWs in anoxic zone. Although Mn-oxidizing bacteria existed in the layer of 30-50 cm with 10³-10⁴ CFU g^-1 dry substate, Mn oxides were only detected at height from 40 to 50 cm with rich oxygen in B-CW. The quantities of bacterial 16S rRNA, amoA, narG and nosZ were not significantly different between two systems (P > 0.05), while Illumina high-throughput sequencing analysis revealed that the abundance of denitrifying bacteria was significant higher in B-CWs, and the abundance of Gammaproteobacteria that have a recognized role in Mn transformation were significantly increased. The results indicated that Mn oxides could enhance TCS and common pollutants removal in both anoxic and aerobic areas through the recycling of Mn between Mn(II) and biogenic Mn oxides.