Weakening of sulfate removal by aquatic plants in iron-based constructed wetlands: The rhizosphere is a sink or source of sulfur?

The fate of sulfur (S) was controlled by a complex interaction of abiotic and microbial reactions in constructed wetlands (CWs). Although zero-valent iron (ZVI) was generally considered to promote nitrogen (N) and S cycle by providing electrons, but its binding effect on sulfate (SO42--S) removal with the rhizosphere oscillating redox conditions had not been determined. This study found that the presence of plants increased SO42-_S removal in Con-CW, while decreased it by 3.93 % in ZVI-CW accompanied by the decrease of S content in the rhizosphere substrates. The enrichment of S oxidation genes (soxA/Y and yedZ), organic S decomposition genes (aslA) and plants radial oxygen loss (ROL) accelerated the transformation of solid-phase S to SO42--S, resulting in ZVI-CW turn from S sink to S source. Overall, the source-sink transformation provided a theoretical guidance for comprehending S cycling in CWs.

Influence of iron species on the simultaneous nitrate and sulfate removal in constructed wetlands under low/high COD concentrations.

Nitrate and sulfate are crucial factors of eutrophication and black and odorous water in the surface water and thus have raised increasing environmental concerns. Constructed wetlands (CWs) are the last ecological barrier before effluent enters the natural water body. To explore the simultaneous removal of nitrate and sulfate, the CW microcosms of CW-Con (with quartz sand), CW-ZVI (quartz sand and zero-valent iron), CW-Mag (quartz sand and magnetite), CW-ZVI + Mag (quartz sand, ZVI and magnetite) groups were set up under the low (100 mg/L)/high (300 mg/L) chemical oxygen demand (COD) concentration. Under the high COD condition, CW-ZVI group showed the best performance in nitrate (97.1%) and sulfate (96.9%) removal. Under the low COD concentration, the removal content of nitrate and sulfate in CW-ZVI group was better than CW-Mag group. The reason for this result was that zero-valent iron (ZVI) could be the electron donor for nitrate and sulfate reduction. Meanwhile, ZVI promoted chemical denitrification under high COD concentration according to PCA analysis. In addition, the produced sulfides inhibited the relative abundance of denitrifying bacteria, resulting in the lowest nitrate removal rate in CW-Mag group with sufficient electron donors. This study provided an alternative method to enhance simultaneous sulfate and nitrate removal in CWs.

Comprehensive evaluation of manganese oxides and iron oxides as metal substrate materials for constructed wetlands from the perspective of water quality and greenhouse effect.

Manganese oxides and iron oxides have been widely introduced in constructed wetlands (CWs) for sewage treatment due to their extensiveness in nature and their ability to participate in various reactions, but their effects on greenhouse gas (GHG) emissions remain unclear. Here, a set of vertical subsurface-flow CWs (Control, Fe-VSSCWs, and Mn-VSSCWs) was established to comprehensively evaluate which are the better metal substrate materials for CWs, iron oxides or manganese oxides, through water quality and the global warming potential (GWP) of nitrous oxide (N2O), methane (CH4), and carbon dioxide (CO2). The results revealed that the removal efficiencies of chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP) in Mn-VSSCWs were all higher than that in Fe-VSSCWs, and manganese oxides could almost completely suppress the CH4 production and reduce GWP (from 8.15 CO2-eq/m2/h to 7.17 mg CO2-eq/m2/h), however, iron oxides promoted GWP (from 8.15 CO2-eq/m2/h to 10.84 mg CO2-eq/m2/h), so manganese oxides are the better CW substrate materials to achieve effective sewage treatment while reducing the greenhouse gas effect.

A new insight on the effects of iron oxides and dissimilated metal-reducing bacteria on CH4 emissions in constructed wetland matrix systems.

Iron oxides and dissimilated metal-reducing bacteria (DMRB) have been reported to result in a reduction in methane (CH4) emissions in constructed wetlands (CWs), but their mechanisms on CH4 production and oxidation remains unclear. Here, a set of CW matrix systems (Control, Fe-CWs, and FeB-CWs) was established to analyze the CH4 emission reduction from various angles, including the valencies of iron, microbial community structure and enzyme activity. The results revealed that the addition of iron oxides promoted the electron transfer between methanogens and Geobacter to promote CH4 production, but it was interesting that iron oxides also reduced the enzymes involved in the carbon dioxide (CO2) reduction pathway and promoted the enzymes that participated in anaerobic oxidation of methane (AOM) thereby leading to the overall reduction in CH4 emissions. Moreover, DMRB could promote iron reduction thereby further reducing CH4 emissions by promoting AOM and competing with methanogens for organic substrates.

In situ fabrication of dynamic self-optimizing Ni3S2 nanosheets as an efficient catalyst for the oxygen evolution reaction.

In this work, a dynamic self-optimizing material consisting of nickel-sulfide nanosheets anchored onto Ni foam (DSO-Ni3S2-NF) as the model material was constructed using a hydrothermal method, and its electrocatalytic performance for oxygen evolution was evaluated. It was found that the electrocatalytic activity of the dynamic self-optimizing (DSO) 25 h-Ni3S2-NF for oxygen evolution is significantly enhanced compared with that of pristine 0 h-Ni3S2-NF since the formed oxide layer evolves into new active sites and the specific process of activity optimization was explored dynamically. The best oxygen evolution reaction (OER) performance was achieved by 25 h-Ni3S2-NF catalyst, which required merely 241 mV overpotential to deliver a current density of 20 mA cm-2, and its Tafel slope was as low as ∼40 mV dec-1, which was superior to most nickel-based catalysts, in 1 M KOH electrolyte. The current density was found to be increased gradually at the same potential and the stability test curves were steady with ignorable decline, showing that the promising strategy of the preparation of a dynamic self-optimizing pre-catalyst may open a new pathway to prepare low-cost, high-performance and stable water splitting catalysts.

The in situ etching assisted synthesis of Pt-Fe-Mn ternary alloys with high-index facets as efficient catalysts for electro-oxidation reactions.

Pt-Based alloys enclosed with high-index facets (HIFs) generally show much higher specific catalytic activities than their counterparts with low-index facets in electro-catalytic reactions. However, the exposure of a certain Pt surface would require a well-defined nanostructure, which usually can only be obtained at larger sizes. Therefore, a low dispersion of Pt atoms in Pt-based alloys with HIFs would affect the atomic utilization of Pt, resulting in most of these Pt-based alloys exhibiting lower mass activity than commercial Pt/C and Pt black catalysts for electro-catalytic reactions. Herein, we address a novel strategy to divide the surface areas of larger sized nanocrystals into small surface area nanocrystals by in situ etching Pt-Fe-Mn concave cubes (CNCs) while maintaining the morphology of the Pt-Fe-Mn alloys to improve the utilization of Pt atoms and thus increase the mass activity. Remarkably, the Pt-Fe-Mn unique concave cube (UCNC) nanocrystals (NCs) showed much higher specific and mass activities toward the methanol oxidation reaction (MOR) than the Pt-Fe-Mn CNCs, commercial Pt black and Pt/C. The kinetic analysis from Tafel plots indicated that UCNC Pt-Fe-Mn NCs had the lowest Tafel slope at whole potentials and the splitting of the first C-H bond of a CH3OH molecule with the first electron transfer was the rate-determining step at high potentials (above 0.45 V). In situ Fourier transform infrared reflection (FTIR) spectroscopic investigation at the molecular level indicated that methanol chemical absorption took place at a low potential of -0.2 V at the UCNC NC electrode. Meanwhile, much higher CO2 productivity was observed at the UCNC NC electrode, indicating the strong anti-poisoning ability of the UCNC Pt-Fe-Mn NCs during methanol electrooxidation. Furthermore, in the formic acid oxidation (FAOR) test, the activity and long-term durability of the Pt-Fe-Mn UCNC NCs were also found to be superior to those of the Pt-Fe-Mn CNCs, commercial Pt black and Pt/C. The enhanced catalytic performance in both the MOR and FAOR is most probably due to the unique HIF structure consisting of small sized particles, enhanced Pt utilization, the richness of crystalline defects and synergetic effects of Pt, Fe, and Mn metals. Our present work provides an insight into the rational design of Pt based alloys with HIFs to improve the catalytic performance of electro-catalytic reactions for fundamental study.