The OH production by adding magnetite (MGT) alone has been reported in composting. However, the potential of nitrilotriacetic acid (NTA) addition for magnetite-amended sludge composting remained unclear. Three treatments with different addition [control check (CK); T1: 5 % MGT; T2: 5 % MGT + 5 % NTA] were investigated to characterize hydroxyl radical, humification and bacterial community response. The NTA addition manifested the best performance, with the peak OH content increase by 52 % through facilitating the cycle of Fe(Ⅱ)/Fe(Ⅲ). It led to the highest organic matters degradation (22.3 %) and humic acids content (36.1 g/kg). Furthermore, NTA addition altered bacterial community response, promoting relative abundances of iron-redox related genera, and amino acid metabolism but decreasing carbohydrate metabolism. Structural equation model indicated that temperature and Streptomyces were the primary factors affecting OH content. The study suggests that utilizing chelators is a promising strategy to strengthen humification in sewage sludge composting with adding iron-containing minerals.

Lead (Pb) can enter soil environment during flooding events such as surface runoff and intensive rainfall. However, the key transformation processes of exogenous Pb during anoxic-oxic alteration remain poorly understood particularly how phosphorus and organic matter contribute to Pb immobilization/release. Here, a kinetic model was established to investigate the Pb transformation in an acidic soil with two levels of Pb contamination under alternating anoxic-oxic conditions, based on the results of seven-step sequential extraction, dissolved organic carbon, sulfate, iron, phosphorus, and surface sites. Results showed that the potentially available Pb, including dissolved, exchangeable, and specifically adsorbed fractions, was gradually transferred to the fulvic complex, Fe-Mn oxides bound, and sulfides bound Pb after 40-day incubation under anoxic conditions, while the fulvic complex Pb further increased after 20-day incubation under oxic conditions. The concentration of phosphorus that was extracted by 0.5 M HCl or 0.03 M NH4F in 0.025 M HCl increased under anoxic conditions and decreased under oxic conditions. When Pb-binding to phosphorus is considered during kinetic modeling, the simulated results of Pb transformation suggest that phosphorus is more important than organic matter for Pb immobilization under anoxic conditions, while the phosphates, Fe-Mn oxides, and sulfides immobilized Pb is slowly released and then complexed by fulvic acids during the re-immobilization of dissolved organic matter in soil under oxic conditions. The model established with low Pb level has been successfully applied to describe the Pb transformation with high Pb level. This study provides a comprehensive understanding of the roles of phosphorus and organic matter in controlling Pb transformation in soil from kinetic modeling.

The heterogeneous-homogeneous coupled Fenton (HHCF) processes combine the advantages of rapid reaction and the catalyst reuse, which makes them attractive for wastewater treatment. Nevertheless, the lack of both, cost-effective catalysts and the desirable Fe3+/Fe2+ conversion mediators limit the development of HHCF processes. This study investigates a prospective HHCF process, in which solid waste copper slag (CS) and dithionite (DNT) act as catalyst and mediator of Fe3+/Fe2+ transformation, respectively. DNT enables controlled leaching of iron and a highly efficient homogeneous Fe3+/Fe2+ cycle by dissociating to SO2- • under acidic conditions, leading to the enhanced H2O2 decomposition and •OH generation (from 48 μmol/L to 399 μmol/L) for p-chloroaniline (p-CA) degradation. The removal rate of p-CA in the CS/DNT/H2O2 system increased by 30 times in comparison with the CS/H2O2 system (increased from 1.21 × 10-3 min-1 to 3.61 × 10-2 min-1). Moreover, batch dosing of H2O2 can greatly promote the yield of •OH (from 399 μmol/L to 627 μmol/L), by mitigating the side reactions between H2O2 and SO2- •. This study highlights the importance of the iron cycle regulation for improvement of the Fenton efficiency and develops a cost-effective Fenton system for organic contaminants elimination in wastewater.

A green, high-efficiency, and wide pH tolerance water remediation process has been urgently acquired for the increasingly exacerbating contaminated water. In this study, a Fe3+/persulfate (Fe3+/PS) system was employed and enhanced with a green natural ligand cysteine (Cys) for the degradation of quinclorac (QNC). The introduction of Cys into the Fe3+/PS system widened the effective pH range to 9 with a superior removal rate for QNC. The mechanism revealed that the Fe3+/Cys/PS system can enhance the ability of degrading QNC by accelerating the Fe3+/Fe2+ redox cycle, maintaining Fe2+ concentration and thereby generating more HO• and SO4•-. The impact factors (i.e., pH, concentrations of PS, Fe3+ and Cys) were optimized as well. This work provides a promising strategy with high catalytic activity and wide pH tolerance for organic contaminated water remediation.

The coexistence of multiple pollutants and lack of carbon sources are challenges for the biological treatment of wastewater. To achieve simultaneous removal of nitrate (NO3--N) and cadmium (Cd2+) at low carbon to nitrogen (C/N) ratios, 2-hydroxy-1,4-naphthoquinone (HNQ) was selected from three redox mediators as an accelerator for denitrification of heterotrophic strain Pseudomonas stutzeri sp. GF2 and autotrophic strain Zoogloea sp. FY6. Then, halloysite nanotubes immobilized with 2-hydroxy-1,4-naphthoquinone (HNTs-HNQ) were prepared and a bioreactor was constructed with immobilized redox mediator granules (IRMG) as the carrier, which was immobilized with HNTs-HNQ and inoculated with the two strains. The immobilized HNQ and the inoculated strains jointly improved the removal ability of NO3--N and Cd2+ and the removal efficiency of NO3--N (25.0 mg L-1) and Cd2+ (5.0 mg L-1) were 92.81% and 93.94% at C/N = 1.5 and hydraulic retention time (HRT) = 4 h. The Cd2+ was removed by adsorption of iron oxides (FeO(OH) and Fe3O4) and IRMG. The electron transport system activity (ETSA) of bacteria was improved and the composition of dissolved organic matter in the effluent was not affected by HNQ. The HNQ promoted the production of FeO(OH) and up-regulated the proportion of Zoogloea (54.75% in the microbial community), indicating that Zoogloea sp. FY6 was dominant in the microbial community. In addition, HNQ influenced the metabolic pathways and improved the relative abundance of some genes involved in nitrogen metabolism and the iron redox cycle.

Microbial extracellular electron transfer (EET) to solid-state electron acceptors such as anodes and metal oxides, which was originally identified in dissimilatory metal-reducing bacteria, is a key process in microbial electricity generation and the biogeochemical cycling of metals. Although it is now known that photosynthetic microorganisms can also generate (photo)currents via EET, which has attracted much interest in the field of biophotovoltaics, little is known about the reduction of metal (hydr)oxides via photosynthetic microbial EET. The present work quantitatively assessed the reduction of ferrihydrite in conjunction with the EET of the photosynthetic microbe Synechocystis sp. PCC 6803. Microbial reduction of ferrihydrite was found to be initiated in response to light but proceeded at higher rates when exogenous glucose was added, even under dark conditions. These results indicate that current generation from Synechocystis cells does not always need light irradiation. The qualitative trends exhibited by the ferrihydrite reduction rates under various conditions showed significant correlation with those of the microbial currents. Notably, the maximum concentration of Fe(II) generated by the cyanobacterial cells under dark conditions in the presence of glucose was comparable to the levels observed in the photic layers of Fe-rich microbial mats.

Conventional water treatment methods are difficult to remove stubborn pollutants emerging from surface water. Advanced oxidation processes (AOPs) can achieve a higher level of mineralization of stubborn pollutants. In recent years, the Fenton process for the degradation of pollutants as one of the most efficient ways has received more and more attention. While homogeneous catalysis is easy to produce sludge and the catalyst cannot be cycled. In contrast, heterogeneous Fenton-like reaction can get over these drawbacks and be used in a wider range. However, the reduction of Fe (III) to Fe(II) by hydrogen peroxide (H2O2) is still the speed limit step when generating reactive oxygen species (ROS) in heterogeneous Fenton system, which restricts the efficiency of the catalyst to degrade pollutants. Based on previous research, this article reviews the strategies to improve the iron redox cycle in heterogeneous Fenton system catalyzed by iron materials. Including introducing semiconductor, the modification with other elements, the application of carbon materials as carriers, the introduction of metal sulfides as co-catalysts, and the direct reduction with reducing substances. In addition, we also pay special attention to the influence of the inherent properties of iron materials on accelerating the iron redox cycle. We look forward that the strategy outlined in this article can provide readers with inspiration for constructing an efficient heterogeneous Fenton system.

The heterogeneous catalytic process has been under development for aqueous pollutant degradation, yet electron transfer efficiency often limits the effectiveness of catalytic reactions. In this study, a novel composite material, manganese doped iron-carbon (Mn-Fe-C), was tailor designed to promote the catalytic electron transfer. The Mn-Fe-C composite, synthesized via a facile carbothermal reduction method, was characterized and evaluated for its performance to activate persulfate (PS) and degrade Rhodamine Blue (RhB) dye under different pH, catalyst dosages, PS dosages, and pollutant concentrations. Electron spin resonance, along with quenching results by ethanol, tert-butanol, phenol, nitrobenzene and benzoquinone, indicated that surface bounded SO4•- was the main contributor for RhB degradation, while the roles of aqueous SO4•- and •OH were very minor. Through characterization by XRD, XPS and FTIR analysis, it was determined that the electron transfer during activation of PS was accelerated by the oxygen functional groups on catalyst surface and the promoted redox cycle of Fe3+ and Fe2+ by Mn. Finally, the Mn-Fe-C composite catalyst exhibited an excellent reusability and stability with negligible leached Fe and Mn ions in solutions. Results of this study provide a promising design for heterogeneous catalysts that can effectively activate PS to remove organic pollutants from water at circumneutral pH conditions.

Fenton reaction is widely used for hazardous pollutant degradation. Reducing agents (RAs) have been proven to be efficient in promoting the generation of HO• in Fenton reaction by accelerating the redox cycle of Fe3+/Fe2+. However, the roles of different RAs in Fenton reaction remain unrevealed. In this work, the catalytic activity of three RAs, i.e., hydroxylamine (NH2OH), ascorbic acid (AA) and cysteine (Cys), on the degradation of benzoic acid (BA) and the hydroxyl radical formation in the Fenton-RAs system were investigated. Results show the catalytic performance of RAs in BA degradation by Fenton reaction followed an order of NH2OH > AA > Cys. Compared with the conventional Fenton system, the effective pH range in the Fenton-NH2OH system extended from 3.0 to 5.0, while the optimal pH in the Fenton-AA and Fenton-Cys systems ranged from 3.0 to 4.0. The Fenton-AA system exhibited a two-stage reaction toward BA degradation, which was different from the Fenton-NH2OH and Fenton-Cys systems. Furthermore, the dosing manner of AA was found to be a key factor governing its role in the Fenton-AA system. This observation suggests the different mechanisms behind the enhancement of the three RAs in Fenton system. Different from NH2OH and Cys, AA would inhibit the generation of HO•, especially at the fast stage of degradation process, where Fe3+ has not accumulated yet. In addition, the economic analysis using the electrical energy per order indicates Fenton-NH2OH system was economically feasible with the lowest energy input, compared to Fenton-AA and Fenton-Cys systems. These results are useful to better understand the roles of RAs in Fenton system, and also provide guidance about the selection and dosing manner of suitable RAs in the advanced oxidation processes.

The sustained oxidation of aqueous organic pollutants using hydroxyl radicals (HO) generated in the UV-irradiated solution of ferric ions was investigated in the presence of Cr(VI). The synergistic effect of simultaneous 4-chlorophenol (4-CP) oxidation and Cr(VI) reduction is explained in terms of the various roles of OH radical, degradation intermediates, and Fe3+/Fe2+ redox cycle. The photolysis of FeIII(OH)2+ generates OH radical which degrades the organic substrate. The reduction of Cr(VI) was inhibited by the OH radical-induced re-oxidation of Cr(III) in the absence of 4-CP. The complete removal of Cr(VI) was achieved only in the presence of phenolic substrates which not only reacts with OH radical (hence inhibiting the reoxidation of Cr(III)) but also generates reducing intermediates which effectively reduce Cr(VI). Fe2+ also converted Cr(VI) to Cr(III) with regenerating Fe3+, which makes the overall process photocatalytic. The photocatalytic activity for the simultaneous removal of 4-CP and Cr(VI) was largely maintained up to five cycles. Such simultaneous and synergic photoactivity was also observed for other phenolic compounds (4-bromophenol, 4-nitrophenol, phenol). The simultaneous and synergic removal of phenolic compounds and Cr(VI) can be enabled through the redox couple of Fe3+/Fe2+ working as a homogeneous photocatalyst.