Microbial nitrogen (N) removal capability can be significantly enhanced in a horizontal subsurface flow constructed wetland (HSCW) amended by Fe-modified biochar (FeB). To further explore the microbiological mechanism of FeB enhancing N removal, nirS- and nirK-denitrifier community diversities, as well as spatial distributions of denitrifiers and anaerobic ammonium oxidation (anammox) bacteria, were investigated in HSCWs (C-HSCW: without biochar and FeB; B-HSCW: amended by biochar; FeB-HSCW: amended by FeB) treating tailwater from a wastewater treatment plant, with C-HSCW without biochar and FeB and B-HSCW amended by biochar as control. The community structures of nirS- and nirK-denitrifiers in FeB-HSCW were significantly optimized for improved N removal compared with the two other HSCWs, although no significant differences in their richness and diversity were detected among the HSCWs. The spatial distributions of the relative abundance of genes involved in denitrification and anammox were more heterogeneous and complex in FeB-HSCW than those in other HSCWs. More and larger high-value patches were observed in FeB-HSCW. These revealed that FeB provides more appropriate habitats for N-removing microorganisms, which can prompt the bacteria to use the habitats more differentially, without competitive exclusion. Overall, the Fe-modified biochar enhancement of the microbial N-removal capability of HSCWs was a result of optimized microbial community structures, higher functional gene abundance, and improved spatial distribution of N-removing microorganisms.
Nitric acid (HNO3) modified biochar (NBC) has been demonstrated to be a promising sorbent. However, the roles of their redox-active moieties (RAMs, i.e., environmentally persistent free radicals (EPFRs) and oxygen-containing function groups) in Cr(VI) removal under varying pH and O2 conditions remain poorly understood. In this study, HNO3 oxidation caused an obvious increase in specific surface area, porous volume, RAMs content, and surface potential of the biochar, leading to the more effective removal of Cr(VI) (with the removal rate reached 100% at pH 2.0) than that of the untreated biochar. Kinetics experiments revealed that O2 and pH are of great importance for the reduction efficiency and rate of Cr(VI). RAMs on NBC can either directly reduce Cr(VI)(predominant pathway) or activate O2 to produce •O2− for indirect Cr(VI) reduction. In addition, we examined the changes in the compositions of RAMs during the reaction by tuning the RAMs compositions using methanol and hydrogen peroxide. The results of electron paramagnetic resonance and X-ray photoelectron spectroscopy analysis demonstrated that the main electron donors on NBC were different at different pH values: oxygen-containing groups, e.g., –OH and C–O–C, played a dominant role in reducing Cr(VI) under acidic conditions while the neutral condition was beneficial to EPFRs-dominated reduction. This study investigated the roles of the EPFRs and oxygen-containing function groups on HNO3 modified biochar, which may provide new insights into the promoted reduction of Cr(VI) by applications of biochar.
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