Algae promotes the biogenic oxidation of Mn(II) by accelerated extracellular superoxide production.

Microbial manganese (Mn) oxidation, predominantly occurs within the anaerobic-aerobic interfaces, plays an important role in environmental pollution remediation. The anaerobic-aerobic transition zones, notably riparian and lakeside zones, are hotspots for algae-bacteria interactions. Here, we adopted a Mn(II)-oxidizing bacterium Pseudomonas sp. QJX-1 to investigate the impact of algae on microbial Mn(II) oxidation and verify the underlying mechanisms. Interestingly, we achieved a remarkable enhancement in bacterial Mn(II)-oxidizing activity within the algae-bacteria co-culture, despite the inability to oxidize Mn(II) for the algae used in this study. In addition, the bacterial density almost remains constant in the presence of algal cells. Therefore, the increased Mn(II) oxidation by QJX-1 in the presence of algae cannot be due to the increased biomass. Within this co-culture system, the Mn(II) oxidation rate surged to an impressive 0.23 mg/L/h, in stark contrast to 0.02 mg/L/h recorded within pure QJX-1 system. The presence of algae could inhibit the Fe-S cluster activity of QJX-1 by the produced active substance in co-culture, and result in the acceleration of extracellular superoxide production due to the impairment of electron transfer functions located in QJX-1 cell membranes. Moreover, elevated peroxidase gene expression and heightened extracellular catalase activity not only expedited Mn(II) ions oxidation but also facilitated conversion of intermediate Mn(III) ions into microbial Mn oxides, achieved through the degradation of hydrogen peroxide. Therefore, the acceleration of extracellular superoxide production and the decomposition of hydrogen peroxide are identified as the principal mechanisms behind the observed enhancement in Mn(II) oxidation within algae-bacteria co-cultures. Our findings highlight the need to consider the effect of algae on microbial Mn(II) oxidation, which plays an important role in the environmental pollution remediation.

Ultrasonication as anaerobic digestion pretreatment to improve sewage sludge methane production: Performance and microbial characterization.

A large amount of sludge is inevitably produced during sewage treatment. Ultrasonication (US) as anaerobic digestion (AD) pretreatment was implemented on different sludges and its effects on batch and semi-continuous AD performance were investigated. US was effective in sludge SCOD increase, size decrease, and CH4 production in the subsequent AD, and these effects were enhanced with an elevated specific energy input. As indicated by semi-continuous AD experiments, the mean daily CH4 production of US-pretreated A2O-, A2O-MBR-, and AO-AO-sludge were 176.9, 119.8, and 141.7 NmL/g-VSadded, which were 35.1%, 32.1% and 78.2% higher than methane production of their respective raw sludge. The US of A2O-sludge achieved preferable US effects and CH4 production due to its high organic content and weak sludge structure stability. In response to US-pretreated sludge, a more diverse microbial community was observed in AD. The US-AD system showed negative net energy; however, it exhibited other positive effects, e.g., lower required sludge retention time and less residual total solids for disposal. US is a feasible option prior to AD to improve anaerobic bioconversion and CH4 yield although further studies are necessary to advance it in practice.

Demulsification with simultaneous water purification by coupling filtration and enhanced oil droplet coalescence at anode interface in an electrochemical reactor.

With the increasing demand of recycling disposal of industrial wastewater, oil-in-water (O/W) emulsion has been paid much attention in recent years owing to its high oil content. However, due to the presence of surfactant and salt, the emulsion was usually stable with complex physicochemical interfacial properties leading to increased processing difficulty. Herein, a novel flow-through electrode-based demulsification reactor (FEDR) was well designed for the treatment of saline O/W emulsion. In contrast to 53.7% for electrical demulsification only and 80.3% for filtration only, the COD removal efficiency increased to 92.8% under FEDR system. Moreover, the pore size of electrode and the applied voltage were two key factors that governed the FEDR demulsification performance. By observing the morphology of oil droplets deposited layer after different operation conditions and the behavior of oil droplets at the electrode surface under different voltage conditions, the mechanism was proposed that the oil droplets first accumulated on the surface of flow-through electrode by sieving effect, subsequently the gathered oil droplets could further coalesce with the promoting effect of the anode, leading to a high-performing demulsification. This study offers an attractive option of using flow-through electrode to accomplish the oil recovery with simultaneous water purification.

Sustainable wastewater treatment and reuse in space.

Exploring the vast extraterrestrial space is an inevitable trend with continuous human development. Water treatment and reuse are crucial in the limited and closed space that is available in spaceships or long-term use space bases that will be established in the foreseeable future. Dedicated water treatment technologies have experienced iterative development for more than 60 years since the first manned spaceflight was successfully launched. Herein, we briefly review the related wastewater characteristics and the history of water treatment in space stations, and we focus on future challenges and perspectives, aiming at providing insights for optimizing wastewater treatment technologies and closing the water cycle in future.

Spatiotemporal dynamics of reactive oxygen species and its effect on beta-blockers' degradation in aquatic plants' rhizosphere.

The pathway for pollutant degradation involving reactive oxygen species (ROS) in the rhizosphere is poorly understood. Herein, a rootchip system was developed to pinpoint the ROS hotspot along the root tip of Iris tectorum. Through mass balance analysis and quenching experiment, we revealed that ROS contributed significantly to rhizodegradation for beta-blockers, ranging from 22.18 % for betaxolol to 83.83 % for atenolol. The identification of degradation products implicated ROS as an important agent to degrade atenolol into less toxic transformation products during phytoremediation. Moreover, an active production of ROS in rhizosphere was identified by mesocosm experiment. Across three root-associated regions aquatic plants inhabiting the rhizosphere accumulated the highest •OH of ∼1200 nM after 3 consecutive days, followed by rhizoplane (∼230 nM) and bulk environment (∼60 nM). ROS production patterns were driven by rhizosphere chemistry (Fe and humic substances) and microbiome variations in different rhizocompartments. These findings not only deepen understanding of ROS production in aquatic plants rhizosphere but also shed light on advancing phytoremediation strategies.

Response of Ionic Hydration Structure and Selective Transport Behavior to Aqueous Solution Chemistry during Nanofiltration.

The effect of aqueous solution chemistry on the ionic hydration structure and its corresponding nanofiltration (NF) selectivity is a research gap concerning ion-selective transport. In this study, the hydration distribution of two typical monovalent anions (Cl- and NO3-) under different aqueous solution chemical conditions and the corresponding transmembrane selectivity during NF were investigated by using in situ liquid time-of-flight secondary ion mass spectrometry in combination with molecular dynamics simulations. We demonstrate the inextricable link between the ion hydration structure and the pore steric effect and further find that ionic transmembrane transport can be regulated by breaking the balance between the hydrogen bond network (i.e., water-water) and ion hydration (i.e., ion-water) interactions of hydrated ion. For strongly hydrated (H2O)nCl- with more intense ion-water interactions, a higher salt concentration and coexisting ion competition led to a larger hydrated size and, thus, a higher ion rejection by the NF membrane, whereas weakly hydrated (H2O)nNO3- takes the reverse under the same conditions. Stronger OH--anion hydration competition resulted in a smaller hydrated size of (H2O)nCl- and (H2O)nNO3-, showing a lower observed average hydration number at pH 10.5. This study deepens the long-overlooked understanding of NF separation mechanisms, concerning the hydration structure.

Comparison of perfluoroalkyl substance adsorption performance by inorganic and organic silicon modified activated carbon.

Owing to the persistence and increasingly stringent regulations of perfluoroalkyl substances (PFAS), it is necessary to improve their adsorption capacities using activated carbon (AC). However, their adsorption capacities are suppressed by dissolved organic matter (DOM). In this study, two ACs modified with organic silicon (C-OS) and inorganic silicon (C-IS) were synthesized and used for the adsorption of PFAS in raw water (RW). The results showed that the PFAS adsorption capacity of C-IS was much less influenced by DOM than that of the original AC (C-virgin). In RW, perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) adsorption capacities on C-IS were 15.08 and 3.65 times higher than those on C-virgin, respectively. DOM had less influence on the PFOA and PFOS adsorption kinetics of C-IS than C-OS and C-virgin. Under multi-PFAS condition, C-IS also exhibited slower desorption of short-chain PFAS and breakthrough in batch and column tests, respectively. Characterization of the ACs before and after adsorption and independent gradient modelling indicated that hydrogen bond interactions between the O-Si of C-IS and the -COOH or -CSO3H groups of PFAS contributed to PFAS adsorption. Density functional theory calculations demonstrated that the adsorption energy of C-IS was much lower than that of C-OS and C-virgin. The arrangement of PFAS molecules on C-OS was chaotic owing to the hydrophobic siloxane chain, whereas the arrangement of PFAS on C-IS was orderly in multi-layer or semi-micelle status and more favorable to PFAS adsorption. This study provides a new strategy for avoiding adverse effects of DOM on PFAS adsorption.

In situ cleaning of foulants by gas scouring on the membrane-electrode in an electro-membrane bioreactor.

Low-maintenance membrane cleaning is essential for the stable operation of membrane bioreactors. This work proposes an in-situ electrical-cleaning method using an electro-MBR. When the applied bias was transiently increased, the membrane flux recovered rapidly because of the scouring effect from gas evolution reactions. The exfoliation of the cake layer induced by gas scouring played a major role in mitigating membrane fouling, recovering the transmembrane pressure (TMP) by 88.6 % under optimal conditions. Membrane modules did not require replacement during the operation period due to the efficacy of electrical cleaning, with the TMP varying between 37.5 % and 62.5 % of the ultimate pressure requiring change of the membrane modules. Despite the increase in power consumption of 0.66 Wh·m-3 due to the additional applied bias, there was no need for chemical additives or manual maintenance. Therefore, the electrical cleaning method enhanced the service life and reduced the maintenance costs of the electro-MBR.

Stress response of Microcystis aeruginosa to chlorine during transportation: The significance of surface-adsorbed organic matter.

The desorption of surface-adsorbed organic matter (S-AOM) without damaging algal cells was reported to be the key to destabilizing Microcystis aeruginosa (M. aeruginosa) cells while avoiding intracellular organic matter (IOM) release in our previous study. However, a temporal effect was found from spontaneous and continuous damage to algal cells even after quenching. This study aims to demonstrate the mechanism of the temporal inactivation effect and the stress response exhibited by chlorine-oxidized algal cells, and finally guide the prechlorination process for algae-laden water at water sources. Chlorine was proved to cause oxidative stress to M. aeruginosa cells, and result in a rapid increase in intracellular reactive oxygen species (ROS) levels. S-AOM appeared to have a protective effect on algal cells against oxidative damage, as evidenced by the maintenance of algal cell integrity and activated antioxidant enzymes. In addition, the activity of Caspase 3, a key protease for the execution of programmed cell death (PCD), was significantly enhanced during prechlorination. Cellular chromatin condensation and DNA fragmentation occurred in the early stages of PCD in algal cells. Therefore, the pre-treatment of algae-laden water at water sources, even with low chlorine doses, can induce a risk of significant algal cell death during the water transfer process due to activation of the PCD process, resulting in a higher health risk for drinking water. These findings indicate that both the dosage of chlorine and the duration of the transportation process should be considered during the prechlorination of algae-laden water, which can provide an important basis for avoiding increasing the risk to drinking water safety.

Synchronous in-situ sludge reduction and enhanced denitrification through improving electron transfer during endogenous metabolisms with Fe(â ¡) addition.

The creation of large amounts of excess sludge and residual nitrogen are critical issues in wastewater biotreatment. This study introduced Fe(II) into an oligotrophic anaerobic reactor (OARFe) that was implemented to modify an anoxic-oxic process to motivate in-situ sludge reduction and enhance denitrification under an effective electron shuttle among organic matter, nitrogen, and Fe. The addition of 15 mg L-1 Fe(II) resulted in a sludge reduction efficiency reached 32.0% with a decreased effluent nitrate concentration of 33.3%. This was mostly attributed to the electron transfer from Fe(II) to organic matters and nitrogen species in OARFe. The participation of Fe(II) led to the upregulation of Geothrix and Terrimonas, which caused active organic matter hydrolysis and cell lysis to stimulate the release of extracellular polymeric substances (EPS) and substance transfer between each layer of EPS. The higher utilization of released bioavailable dissolved organic matter improved endogenous denitrification, which can be combined with iron autotrophic denitrification to realize multiple electron donor-based nitrogen removal pathways, resulting in an increased nitrate removal rate of 58.2% in the absence of external carbon sources. These functional bacteria associated with the transformation of nitrogen and carbon and cycling between ferrous and ferric ions were enriched in OARFe, which contributed to efficient electron transport occurred both inside and outside the cell and increased 2,3,5-triphenyltetrazolium chloride electronic transport system activity by 46.9%. This contributed to the potential operational costs of chemical addition and sludge disposal of Fe-AO being 1.9 times lower than those of conventional A2O processes. These results imply that the addition of ferrous ions to an oligotrophic anaerobic zone for wastewater treatment has the potential for low-cost pollution control.

A Novel Electromagnetic Driving System for 5-DOF Manipulation in Intraocular Microsurgery.

This work presents a novel electromagnetic driving system that consists of eight optimized electromagnets arranged in an optimal configuration and employs a control framework based on an active disturbance rejection controller (ADRC) and virtual boundary. The optimal system configuration enhances the system's compatibility with other ophthalmic surgical instruments, while also improving its capacity to generate magnetic force in the vertical direction. Besides, the optimal electromagnet parameters provide a superior comprehensive performance on magnetic field generation capacity and thermal power. Hence, the presented design achieves a stronger capacity for sustained work. Furthermore, the ADRC controller effectively monitors and further compensates the total disturbance as well as gravity to enhance the system's robustness. Meanwhile, the implementation of virtual boundaries substantially enhances interactive security via collision avoidance. The magnetic and thermal performance tests have been performed on the electromagnet to verify the design optimization. The proposed electromagnet can generate a superior magnetic field of 2.071 mT at a distance of 65 mm with an applied current of 1 A. Moreover, it demonstrates minimal temperature elevation from room temperature (25 °C) to 46 °C through natural heat dissipation in 3 h, thereby effectively supporting prolonged magnetic manipulation of intraocular microsurgery. Furthermore, trajectory tracking experiments with disturbances have been performed in a liquid environment similar to the practical ophthalmic surgery scenarios, to verify the robustness and security of the presented control framework. The maximum root mean square (RMS) error of performance tests in different operation modes remains 35.8 µm, providing stable support for intraocular microsurgery.

Sulfate Doping Promotes Agglomeration of Calcium Fluoride Crystals.

Calcium salt precipitation is an effective solution to wastewater fluoride pollution. The purity and precipitation efficiency of calcium fluoride is critical for its removal and recovery. This study aimed to reveal the role of coexisting sulfates in the precipitation of calcium fluoride. A low sulfate concentration promoted calcium fluoride precipitation. The size of calcium fluoride-aggregated particle clusters increased from 750 to 2000 nm when the molar ratio of sulfate to fluoride was increased from 0 to 3:100. Sulfate doped in the calcium fluoride crystals neutralized the positive charge of the calcium fluoride. Online atomic force microscopy measurements showed that sulfate reduced the repulsive force between calcium fluoride crystals and increased the adhesion force from 1.62 to 2.46 nN, promoting the agglomeration of calcium fluoride crystals. Sulfate improved the precipitation efficiency of calcium fluoride by promoting agglomeration; however, the purity of calcium fluoride was reduced by doping. Sulfate reduced the induction time of calcium fluoride crystallization and improved the nucleation rate of calcium fluoride. Sulfate should be retained to improve the precipitation of calcium fluoride and to avoid its loss from the effluents. However, it is necessary to separate sulfate from fluoride to obtain high-purity calcium fluoride. Therefore, sulfate concentration regulation in high-fluoride wastewater is key to achieving the efficient removal and recovery of fluoride ions.

Can "Risk-Sharing" Mechanisms Help Clonal Aquatic Plants Mitigate the Stress of Nanoplastics?

Most aquatic plants applied to ecological restoration have demonstrated a clonal growth pattern. The risk-spreading strategy plays a crucial role in facilitating clonal plant growth under external environmental stresses via clonal integration. However, the effects of different concentrations of nanoplastics (NPs) on the growth traits of clonal aquatic plants are not well understood. Therefore, this study aimed to investigate the impact of NPs exposure on seedlings of parent plants and connected offspring ramets. A dose response experiment (0.1, 1, and 10 mg L-1) showed that the growth of Eichhornia crassipes (water hyacinth) was affected by 100 nm polystyrene nanoplastics after 28 days of exposure. Tracer analysis revealed that NPs are accumulated by parent plants and transferred to offspring ramets through stolon. Quantification analysis showed that when the parent plant was exposed to 10 mg L-1 NPs alone for 28 days, the offspring ramets contained approximately 13 ± 2 µg/g NPs. In the case of connected offspring ramets, leaf and root biomass decreased by 24%-51% and 32%-51%, respectively, when exposed to NP concentrations ranging from 0.1 to 10 mg L-1. Excessive enrichment of NPs had a detrimental effect on the photosynthetic system, decreasing the chlorophyll content and nonphotochemical quenching. An imbalance in the antioxidant defense systems, which were unable to cope with the oxidative stress caused by NP concentrations, further damaged various organs. The root system can take up NPs and then transfer them to the offspring through the stolon. Interference effects of NPs were observed in terms of root activity, metabolism, biofilm composition, and the plant's ability to purify water. However, the risk-spreading strategy employed by parent plants (interconnected offspring ramets) offered some relief from NP-induced stress, as it increased their relative growth rate by 1 to 1.38 times compared to individual plants. These findings provide substantial evidence of the high NP enrichment capacity of E. crassipes for ecological remediation. Nevertheless, we must also remain aware of the environmental risk associated with the spread of NPs within the clonal system of E. crassipes, and contaminated cloned individuals need to be precisely removed in a timely manner to maintain normal functions.

Space aquatic chemistry: A roadmap for drinking water treatment in microgravity.

Rapid advancement in aerospace technology has successfully enabled long-term life and economic activities in space, particularly in Low Earth Orbit (LEO), extending up to 2000 km from the mean sea level. However, the sustainance of the LEO Economy and its Environmental Control and Life Support System (ECLSS) still relies on a regular cargo supply of essential commodities (e.g., water, food) from Earth, for which there still is a lack of adequate and sustainable technologies. One key challenge in this context is developing water treatment technologies and standards that can perform effectively under microgravity conditions. Solving this technical challenge will be a milestone in providing a scientific basis and the necessary support mechanisms for establishing permanent bases in outer space and beyond. To identify clues towards solving this challenge, we looked back at relevant scientific research exploring novel technologies and standards for deep space exploration, also considering feedback for enhancing these technologies on land. Synthesizing our findings, we share our outlook for the future of drinking water treatment in microgravity. We also bring up a new concept for space aquatic chemistry, considering the closed environment of engineered systems operating in microgravity.

Enhanced oxidation of organic pollutants by regulating the interior reaction region of reactive electrochemical membranes.

Reactive electrochemical membrane (REM) emerges as an attractive strategy for the elimination of refractory organic pollutants that exist in wastewater. However, the limited reaction sites in traditional REMs greatly hinder its practical application. Herein, a feed-through coating methodology was developed to realize the uniform loading of SnO2-Sb catalysts on the interior surface of a REM. The uniformly coated REM (Unif-REM) exhibited 2.4 times higher reaction kinetics (0.29 min-1) than that of surface coated REM (Surf-REM) for the degradation of 2 mM 4-chlorophenol (4-CP), rendering an energy consumption as low as 0.016 kWh gTOC-1. The fast degradation of various emerging contaminants, e.g., sulfamethoxazole (SMX), ofloxacin (OFLX), and tetracycline (TC), also confirms its superior oxidation capability. Besides, the Unif-REM exhibited good performance in generating hydroxyl radicals (•OH) and a relatively long service lifetime. The simulation of spatial current distribution demonstrates that the interior reaction region in the Unif-REM channels can be drastically extended, thereby maximizing the surface coupling of mass diffusion and electron transfer. This study offers an in-depth look at the spatially confined reactions in REM and provides a reference for the design of electrochemical systems with economically efficient water purification.

Advanced treatment of coking wastewater: Recent advances and prospects.

Advanced treatment of refractory industrial wastewater is still a challenge. Coking wastewater is one of coal chemical wastewater, which contains various refractory organic pollutants. To meet the more and more rigorous discharge standard and increase the reuse ratio of coking wastewater, advanced treatment process must be set for treating the biologically treated coking wastewater. To date, several advanced oxidation processes (AOPs), including Fenton, ozone, persulfate-based oxidation, and iron-carbon micro-electrolysis, have been applied for the advanced treatment of coking wastewater. However, the performance of different advanced treatment processes changed greatly, depending on the components of coking wastewater and the unique characteristics of advanced treatment processes. In this review article, the state-of-the-art advanced treatment process of coking wastewater was systematically summarized and analyzed. Firstly, the major organic pollutants in the secondary effluents of coking wastewater was briefly introduced, to better understand the characteristics of the biologically treated coking wastewater. Then, the performance of various advanced treatment processes, including physiochemical methods, biological methods, advanced oxidation methods and combined methods were discussed for the advanced treatment of coking wastewater in detail. Finally, the conclusions and remarks were provided. This review will be helpful for the proper selection of advanced treatment processes and promote the development of advanced treatment processes for coking wastewater.

Enzyme-enhanced acidogenic fermentation of waste activated sludge: Insights from sludge structure, interfaces, and functional microflora.

Anaerobic fermentation is widely installed to recovery valuable resources and energy as CH4 from waste activated sludge (WAS), and its implementation in developing countries is largely restricted by the slow hydrolysis, poor efficiency, and complicate inert components therein. In this study, enzyme-enhanced fermentation was conducted to improve sludge solubilization from 283 to 7728 mg COD/L and to enhance volatile fatty acids (VFAs) yield by 58.6 % as compared to the conventional fermentation. The rapid release of organic carbon species, especially for tryptophan- and tyrosine-like compounds, to outer layer of extracellular polymeric substance (EPS) occurred to reduce the structural complexity and improve the sludge biodegradability towards VFAs production. Besides, upon enzymatic pretreatment the simultaneous exposure of hydrophilic and hydrophobic groups on sludge surfaces increased the interfacial hydrophilicity. By quantitative analysis via interfacial thermodynamics and XDLVO theory, it was confirmed that the stronger hydrophilic repulsion and energy barriers in particle interface enhanced interfacial mass transfer and reactions involved in acidogenic fermentation. Meanwhile, these effects stimulate the fermentation functional microflora and predominant microorganism, and the enrichment of the hydrolytic and acid-producing bacteria in metaphase and the proliferation of acetogenic bacteria, e.g., Rubrivivax (+9.4 %), in anaphase also benefits VFAs formation. This study is practically valuable to recovery valuable VFAs as carbon sources and platform chemicals from WAS and agriculture wastes.

Polydopamine-Modified 2D Iron (II) Immobilized MnPS3 Nanosheets for Multimodal Imaging-Guided Cancer Synergistic Photothermal-Chemodynamic Therapy.

Manganese phosphosulphide (MnPS3 ), a newly emerged and promising member of the 2D metal phosphorus trichalcogenides (MPX3 ) family, has aroused abundant interest due to its unique physicochemical properties and applications in energy storage and conversion. However, its potential in the field of biomedicine, particularly as a nanotherapeutic platform for cancer therapy, has remained largely unexplored. Herein, a 2D "all-in-one" theranostic nanoplatform based on MnPS3 is designed and applied for imaging-guided synergistic photothermal-chemodynamic therapy. (Iron) Fe (II) ions are immobilized on the surface of MnPS3 nanosheets to facilitate effective chemodynamic therapy (CDT). Upon surface modification with polydopamine (PDA) and polyethylene glycol (PEG), the obtained Fe-MnPS3 /PDA-PEG nanosheets exhibit exceptional photothermal conversion efficiency (η = 40.7%) and proficient pH/NIR-responsive Fenton catalytic activity, enabling efficient photothermal therapy (PTT) and CDT. Importantly, such nanoplatform can also serve as an efficient theranostic agent for multimodal imaging, facilitating real-time monitoring and guidance of the therapeutic process. After fulfilling the therapeutic functions, the Fe-MnPS3 /PDA-PEG nanosheets can be efficiently excreted from the body, alleviating the concerns of long-term retention and potential toxicity. This work presents an effective, precise, and safe 2D "all-in-one" theranostic nanoplatform based on MnPS3 for high-efficiency tumor-specific theranostics.

Al and Mn speciation changes during the pre-oxidation with potassium permanganate and coagulation removing natural organic matter and its membrane fouling behavior.

In this study, we systematically explore coagulation behavior, ultrafiltration membrane fouling behavior and the mechanism involved in during the process of pre-oxidation of potassium permanganate and coagulation of aluminum chloride at different condition to treat model pollutants (humic acid, HA) and natural water. The KMnO4 pre-oxidation significantly enhances flocs formation, and for HA artificial water the flocs size increases from 82 to 122 µm at pH 5.5, from 63 to 185 µm at pH 7.0 and from 0 to 75 µm at pH 8.5, respectively, as for natural water it increases from 72 to 139 µm. The enhanced coagulation at pH 5.5 is attributed to the increased polymeric Al speciation after pre-oxidation along with the generated Mn2+ damaging the electric double layer structure. And for pH 8.5 it is mainly caused by the in-situ MnO2 as combination nuclei during pre-oxidation. Besides, for pH 7.0, the combined effect of in-situ MnO2 and the increased polymeric Al speciation both contribute to improvement of the coagulation. What's more, the enhanced Al coagulation by pre-oxidation of KMnO4 also helps alleviate the membrane fouling for both HA artificial water and natural water, and a much rougher surface with larger flocs forms after KMnO4-aided Al coagulation filtration. This study provides an alternative perspective on the mechanism of pre-oxidation coagulation process.

Unveiling the spatially confined oxidation processes in reactive electrochemical membranes.

Electrocatalytic oxidation offers opportunities for sustainable environmental remediation, but it is often hampered by the slow mass transfer and short lives of electro-generated radicals. Here, we achieve a four times higher kinetic constant (18.9 min-1) for the oxidation of 4-chlorophenol on the reactive electrochemical membrane by reducing the pore size from 105 to 7 µm, with the predominate mechanism shifting from hydroxyl radical oxidation to direct electron transfer. More interestingly, such an enhancement effect is largely dependent on the molecular structure and its sensitivity to the direct electron transfer process. The spatial distributions of reactant and hydroxyl radicals are visualized via multiphysics simulation, revealing the compressed diffusion layer and restricted hydroxyl radical generation in the microchannels. This study demonstrates that both the reaction kinetics and the electron transfer pathway can be effectively regulated by the spatial confinement effect, which sheds light on the design of cost-effective electrochemical platforms for water purification and chemical synthesis.