Enhancement of waterborne pathogen removal by functionalized biochar with ε-polylysine ″dynamic arms″: Potential application in ultrafiltration system.

Widespread outbreaks of threatening infections caused by unknown pathogens and water transmission have spawned the development of adsorption methods for pathogen elimination. We proposed a biochar functionalization strategy involving ε-polylysine (PLL), a bio-macromolecular poly(amino acid)s with variable folding conformations, as a "pathogen gripper" on biochar. PLL was successfully bridged onto biochar via polydopamine (PDA) crosslinking. The extension of electropositive side chains within PLL enables the capture of both nanoscale viruses and micrometer-scale bacteria in water, achieving excellent removal performances. This functionalized biochar was tentatively incorporated into ultrafiltration (UF) system, to achieve effective and controllable adsorption and retention of pathogens, and to realize the transfer of pathogens from membrane surface/pore to biochar surface as well as flushing water. The biochar-amended UF systems presents complete retention (∼7 LRV) and hydraulic elution of pathogens into membrane flushing water. Improvements in removal of organics and anti-fouling capability were observed, indicating the broken trade-off in UF pathogen removal dependent on irreversible fouling. Chemical characterizations revealed adsorption mechanisms encompassing electrostatic/hydrophobic interactions, pore filling, electron transfer, chemical bonding and secondary structure transitions. Microscopic and mechanical analyses validated the mechanisms for rapid adsorption and pathogen lysis. Low-concentration alkaline solution for used biochar regeneration, facilitated the deprotonation and transformation of PLL side chain to folded structures (α-helix/ß-sheet). Biochar regeneration process also promoted the effective detachment/inactivation of pathogens and protection of functional groups on biochar, corroborated by physicochemical inspection and molecular dynamics simulation. The foldability of poly(amino acid)s acting like dynamic arms, significantly contributed to pathogen capture/desorption/inactivation and biochar regeneration. This study also inspires future investigation for performances of UF systems amended by poly(amino acid)s-functionalized biochar under diverse pressure, temperature, reactive oxygen species of feeds and chemical cleaning solutions, with far-reaching implications for public health, environmental applications of biochar, and UF process improvement.

Sustained oxidation of Tea-Fe(III)/H2O2 simultaneously achieves sludge reduction and carbamazepine removal: The crucial role of EPS regulation.

Establishing an economic and sustained Fenton oxidation system to enhance sludge dewaterability and carbamazepine (CBZ) removal rate is a crucial path to simultaneously achieve sludge reduction and harmless. Leveraging the principles akin to "tea making", we harnessed tea waste to continually release tea polyphenols (TP), thus effectively maintaining high level of oxidation efficiency through the sustained Fenton reaction. The results illustrated that the incorporation of tea waste yielded more favorable outcomes in terms of water content reduction and CBZ removal compared to direct TP addition within the Fe(III)/hydrogen peroxide (H2O2) system. Concomitantly, this process mainly generated hydroxyl radical (•OH) via three oxidation pathways, effectively altering the properties of extracellular polymeric substances (EPS) and promoting the degradation of CBZ from the sludge mixture. The interval addition of Fe(III) and H2O2 heightened extracellular oxidation efficacy, promoting the desorption and removal of CBZ. The degradation of EPS prompted the transformation of bound water to free water, while the formation of larger channels drove the discharge of water. This work achieved the concept of treating waste with waste through using tea waste to treat sludge, meanwhile, can provide ideas for subsequent sludge harmless disposal.

Excessive Ozonation Stress Triggers Severe Membrane Biofilm Accumulation and Fouling.

The established benefits of ozone on microbial pathogen inactivation, natural organic matter degradation, and inorganic/organic contaminant oxidation have favored its application in drinking water treatment. However, viable bacteria are still present after the ozonation of raw water, bringing a potential risk to membrane filtration systems in terms of biofilm accumulation and fouling. In this study, we shed light on the role of the specific ozone dose (0.5 mg-O3/mg-C) in biofilm accumulation during long-term membrane ultrafiltration. Results demonstrated that ozonation transformed the molecular structure of influent dissolved organic matter (DOM), producing fractions that were highly bioavailable at a specific ozone dose of 0.5, which was inferred to be a turning point. With the increase of the specific ozone dose, the biofilm microbial consortium was substantially shifted, demonstrating a decrease in richness and diversity. Unexpectedly, the opportunistic pathogen Legionella was stimulated and occurred in approximately 40% relative abundance at the higher specific ozone dose of 1. Accordingly, the membrane filtration system with a specific ozone dose of 0.5 presented a lower biofilm thickness, a weaker fluorescence intensity, smaller concentrations of polysaccharides and proteins, and a lower Raman activity, leading to a lower hydraulic resistance, compared to that with a specific ozone dose of 1. Our findings highlight the interaction mechanism between molecular-level DOM composition, biofilm microbial consortium, and membrane filtration performance, which provides an in-depth understanding of the impact of ozonation on biofilm accumulation.

Polyphenol-mediated defect patching of graphene oxide membranes for sulfonamide contaminants removal and fouling control.

Graphene oxide (GO)-based laminar membranes are promising candidates for next-generation nanofiltration membranes because of their theoretically frictionless nanochannels. However, nonuniform stacking during the filtration process and the inherent swelling of GO nanosheets generate horizontal and vertical defects, leading to a low selectivity and susceptibility to pore blockage. Herein, both types of defects are simultaneously patching by utilizing tannic acid and FeⅢ. Tannic acid first partially reduced the upper GO framework, and then coordinated with FeⅢ to form a metal-polyphenol network covering horizontal defects. Due to the enhanced steric hindrance, the resulting membrane exhibited a two-fold increase in sulfonamide contaminants exclusion compared to the pristine GO membrane. A non-significant reduction in permeance was observed. In terms of fouling control, shielding defects significantly alleviated the irreversible pore blockage of the membrane. Additionally, the hydrophilic metal-polyphenol network weakened the adhesion force between the membrane and foulants, thereby improving the reversibility of fouling in the cleaning stage. This work opens up a new way to develop GO-based membranes with enhanced separation performance and antifouling ability.

Synergistic roles of oxidation and self-aggregation in efficient ultrafiltration membrane fouling alleviation using a flow-through Sb-SnO2 anode during wastewater reclamation.

The application of ultrafiltration (UF) in wastewater reclamation alleviates the demand for limited water supplies. However, the membrane fouling caused by the effluent organic matter (EfOM) becomes a major obstacle for UF application. In this study, a pre-oxidation strategy for UF using a Sb-SnO2 (ATO) anode in flow-through mode was proposed with the hopes to improve the performance of UF during wastewater reclamation. The results indicated that this flow-through ATO (FA) anode significantly outperformed a boron-doped diamond (BDD) anode in terms of EfOM degradation and membrane fouling control. It is noteworthy that apart from oxidation, the self-aggregation behavior of foulants was also involved in the mechanisms of membrane fouling mitigation. On the one hand, FA pre-oxidation relieved the burden of membrane fouling by decomposing the macromolecular EfOM into small molecular organic matter, and even mineralizing it. The effective destruction of unsaturated EfOM by FA pre-oxidation made a remarkable contribution to fouling mitigation due to the strong correlation between the total fouling index and UV254. On the other hand, the surface morphology of membrane and interface properties of foulants revealed the self-aggregation behavior of foulants. FA pre-oxidation made the foulants aggregate spontaneously and reduced the potential of forming a dense cake layer on the membrane surface, which was conductive for water permeation. Overall, FA pre-oxidation proved to be a feasible and chemical-free option for UF pretreatment to simultaneously produce high-quality reused water and alleviate membrane fouling during wastewater reclamation.

Replacing traditional pretreatment in one-step UF with natural short-distance riverbank filtration: Continuous contaminants removal and TMP increase relief.

Scientists have been focusing on applying more natural processes instead of industrial chemicals in drinking water treatment to achieve the purpose of carbon emissions reduction. In this study, we shortened the infiltration range of riverbank filtration, a natural water purification process, to form the short-distance riverbank filtration (sRBF) which retained its ability in water quality improvement and barely influenced the groundwater environment, and integrated it with ultrafiltration (UF) to form a one-step sRBF-UF system. This naturalness-artificiality combination could realize stable contaminants removal and trans-membrane pressure (TMP) increase relief for over 30 days without dosing chemicals. Generally, both sRBF and UF played the important role in river water purification, and the interaction between them made the one-step sRBF-UF superior in long-term operation. The sRBF could efficiently remove contaminants (90 % turbidity, 60 % total nitrogen, 30 % ammonia nitrogen, and 25 % total organic carbon) and reduce the membrane fouling potential of river water under its optimum operation conditions, i.e., a hydraulic retention time of 48 h, an operation temperature of 20 °C, and a synergistic filter material of aquifer and riverbank soil. Synergistic adsorption, interception, and microbial biodegradation were proved to be the mechanisms of contaminants and foulants removal for sRBF. The sequential UF also participated in the reduction of impurities and especially played a role in intercepting microbial metabolism products and possibly leaked microorganisms from sRBF, assuring the safety of product water. To date, the one-step sRBF-UF was a new attempt to combine a natural process with an artificial one, and realized a good and stable product quality in long-term operation without doing industrial chemicals, which made it a promised alternative for water purification for cities alongside the river.

Three-compartment membrane electrolyzer combining simultaneous desalination and oxidative degradation in treating nanofiltration concentrate.

The complex organic and inorganic solutes present in nanofiltration's purification by-product (NF concentrate, NFC) pose challenges to the water processing procedure. To address this, a three-compartment membrane electrolyzer was proposed that facilitates electro-driven ion migration for crystallization alongside synchronous anodic oxidation for organic degradation. With a hydraulic retention time (HRT) of 5 min and a current exceeding 50 mA, the system effectively separated over 25 % of inorganic salts and accomplished reclamation through crystallization in the concentration compartment. Simultaneously, it achieved oxidation of pollutants by more than 35 % based on the total nitrogen index and removed upwards of 15 % of organic carbon. Notably, the efficiency of pollutant removal correlated strongly with the intensity of the current. Furthermore, this study uncovered two issues encountered during the electrochemical process: membrane fouling and electrode fouling. During concentration, metal cations readily formed organic pollution by complexing with organic pollutants, while the crystallization of inorganics on the surface of anion exchange membranes emerged as a pivotal factor hindering current enhancement, similar to the formation of deposited salt in a solution. Long HRT can lead to electrode contamination and corrosion which subsequently affect current efficiency. Energy consumption verified the feasibility of the electrolyzer for NFC processing. Based on our findings, a current intensity of 100 mA (equivalent to a density of 8 mA/cm2) was deemed optimal, striking a balance between pollutant removal and various limiting factors associated with each pollutant. Consequently, this innovative advancement in membrane electrolyzers helps in overcoming limitations in synergistic desalination, ion recovery, and organic removal, establishing a fundamental component of the abbreviated flow process for future NFC treatment.

Surface modification of Feâ ¢-juglone coating on nanofiltration membranes for efficient biofouling mitigation.

Nanofiltration membranes have increasingly played a vital role in the purification of surface water and the recycling of wastewater. However, the problem of membrane biofouling, which leads to shortened service life and increased energy consumption, has hindered the widespread application of nanofiltration membranes. In this study, we developed functionalized nanofiltration membranes with anti-adhesive and anti-biofouling properties by coordinating FeIII and juglone onto commercial nanofiltration membranes in a facile and viable manner. Due to the hydrophilic nature of the FeⅢ-juglone coating as well as its ultra-thin thickness and minimal impact on the membrane pores, the permeance of the optimally modified membrane even increased slightly (14 %). The outstanding anti-adhesive property of the FeⅢ-juglone coating was demonstrated by a significant reduction in the adsorption of proteins and bacteria. Furthermore, the modified membranes exhibited lower flux decline amplitude and reduced biofilm deposition during dynamic fouling experiment, further supporting the outstanding anti-biofouling performance of the nanofiltration membrane after the modification with FeⅢ-juglone coating. This study presents a novel and feasible approach for simultaneously improving the water permeance, anti-adhesive property and anti-biofouling property of commercial nanofiltration membranes.

In-depth study of the removal of Mn(II) by Fe(VI) treatment and the profound influence of NOM on floc formation and properties.

The presence of manganese(II) in drinking water sources poses a significant treatment difficulty for water utilities, thus necessitating the development of effective removal strategies. Treatment by Fe(VI), a combined oxidant and coagulant, has been identified as a potential green solution; however, its effectiveness is hampered by natural organic matter (NOM), and this underlying mechanism is not fully understood. Here, we investigated the inhibitory effect of three different types of NOM, representing terrestrial, aquatic, and microbial origins, on Mn(II) removal and floc growth during Fe(VI) coagulation. Results revealed that Fe(VI) coagulation effectively removes Mn(II), but NOM could inhibit its effectiveness by competing in oxidation reactions, forming NOM-Fe complexes, and altering floc aggregation. Humic acid was found to exhibit the strongest inhibition due to its unsaturated heterocyclic species that strongly bond to flocs and react with Fe(VI). For the first time, this study has presented a comprehensive elucidation of the atomic-level structure of Fe(VI) hydrolysis products by employing Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS). Results demonstrated that NOM strengthened single-corner and double-corner coordination between FeO6 octahedrons that were consumed by Mn(II), resulting in an increased contribution of γ-FeOOH in the core-shell structure (γ-FeOOH shell and γ-F2O3 core), thereby inhibiting coagulation effects. Furthermore, NOM impeded the formation of stable manganite, resulting in more low-valence Mn(III) being incorporated in the form of an unstable intermediate. These findings provide a deeper understanding of the complex interplay between Fe coagulants, heavy metal pollution, and NOM in water treatment and offer insight into the limitations of Fe(VI) in practical applications.

Simulated-sunlight enhances membrane aerated biofilm reactor performance in sulfamethoxazole removal and antibiotic resistance genes reduction.

Membrane aerated biofilm reactors (MABRs) can be used to treat domestic wastewater containing sulfamethoxazole (SMX) because of their favorable performance in the treatment of refractory pollutants. However, biologics are generally subjected to antibiotics stress, which induces the production of antibiotic resistance genes (ARGs). In this study, a simulated-sunlight assisted MABR (L-MABR) was used to promote SMX removal and reduce ARGs production. The SMX removal efficiency of the l-MABR system was 9.62 % superior to that of the MABR system (83.13 %). In contrast from MABR, in the l-MABR, only 28.75 % of SMX was removed through microbial activity because functional bacteria were inactivated through radiation by simulated sunlight. In addition, photolysis (64.61 %) dominated SMX removal, and the best performing indirect photolysis process was the excited state of effluent organic matters (3EfOMs*). Through photolysis, ultraviolet (UV) and reactive oxygen species (ROS) enriched the SMX removal route, resulting in the SMX removal pathway in the l-MABR no longer being limited by enzyme catalysis. More importantly, because of the inactivation of functional bacteria, whether in the effluent or biofilm, the copy number of ARGs in the l-MABR was 1-3 orders of magnitude lower than that in the MABR. Our study demonstrates the feasibility of utilizing simulated-sunlight to enhance the antibiotic removal efficiency while reducing ARG production, thus providing a novel idea for the removal of antibiotics from wastewater.

Photocatalytic membrane coated with α-Fe2O3/Fe3O4 for enhanced filtration performance and antifouling property in surface water treatment.

A photocatalytic membrane coated with α-Fe2O3/Fe3O4 nanoparticles has been developed to address the challenges of membrane fouling and organic removal in the treatment of natural surface water. The photocatalytic and filtration properties of the membranes were investigated through a variety of methods. The successful preparation of iron oxide was confirmed by UV-vis diffuse reflectance spectra and X-ray diffractometry, with α-Fe2O3 identified as the primary photocatalytic agent. A commercial ultrafiltration (UF) membrane was employed as a comparison to evaluate the photocatalytic performance and filtration properties of the modified membrane. Results showed that the photocatalytic membrane achieved better removal rates for UV254 (22.0%) and specific fluorescent organic compounds, such as component 2 (19.38%) and component 3 (16.89%), compared to the control group. Furthermore, both irreversible and reversible fouling resistances of the prepared membranes were significantly lower than that of the control group, with reductions of 39.4% and 50.2%, respectively. The membrane coated with α-Fe2O3/Fe3O4 nanoparticles exhibited moderate removal of protein-like and terrestrially derived humic-like fluorescent organics while controlling membrane fouling. Although the α-Fe2O3/Fe3O4 nanoparticles-coated photocatalytic membrane demonstrated good anti-fouling properties, the removals of organic matters were not as effective as anticipated due to the shorter hydraulic retention time. This study provides valuable insights for enhancing pollutant degradation and anti-fouling properties of membranes through the utilization of solar photocatalytic α-Fe2O3/Fe3O4 surface-modified membranes in the treatment of natural surface water.

Nanofiltration Membranes with Salt-Responsive Ion Valves for Enhanced Separation Performance in Brackish Water Treatment: A Battle against the Limitation of Salt Concentration.

Utilizing brackish water resources has imposed a high requirement on the design and construction of nanofiltration membranes. To overcome the limitation of high salt concentration on the nanofiltration separation performance resulting from the weakened Donnan effect, a nanofiltration membrane with the effect of salt-responsive ion valves was developed by incorporating zwitterionic nanospheres into the polyamide layer (PA-ZNs). The interaction between the nanospheres and membranes at high salinity was revealed through a combination analysis from the perspectives of water transport model, positron annihilation spectroscopy, and solute rejection, contributing to the formation of the valve effect. The PA-ZNs membrane presented a breakthrough in overcoming the limitation of increased salt concentrations on nanofiltration separation performance, achieving a high selectivity of 105 for mono/multivalent anions. To reveal the role of the ion valve effect in ion transport through the membrane, the membrane conductance was determined at different salt concentrations, confirming channel-controlled transport at low salinity and ion valve-controlled transport at high salinity. Moreover, the main membrane separation mechanisms were systematically studied. The concept of salt-responsive ion valves may contribute to expanding the application of nanofiltration in brackish water treatment.

New insights into the influence of pre-oxidation on membrane fouling during nanofiltration of brackish water considering inorganic-organic complexation and oxidant reduction byproducts.

Even though pre-oxidation is usually considered as a promising method to alleviate membrane fouling, information on performance and inner mechanisms of pre-oxidation-influenced membrane fouling during nanofiltration of brackish water is still limited. This study is the first work in which oxidant reduction byproducts and interaction between different pollutants were particularly considered to address these problems. Herein, nanofiltration experiments with different pre-oxidized synthesis brackish water containing inorganic salts and organic pollutants were conducted. Membrane flux results showed that both NaClO and K2FeO4 aggravated membrane fouling, but 0.45 mg/mg TOC KMnO4 mitigated it when simulation results of NICA-Donnan model showed that the complexation between calcium ions and humic acid (HA) was weakened. However, membrane fouling was enhanced by higher dosage of KMnO4. Fourier transform infrared spectrometer using attenuated total reflection (ATR-FTIR) and X-ray diffraction (XRD) spectrum showed that the aggravated membrane fouling was mainly caused by the generation of amorphous manganese oxide, which was oxidant reduction byproduct and had strong capacity for adsorption of HA. Particle size distribution and zeta potential variation indicated that the accumulation of HA could enhance the crystallization process and then the electrostatic attraction between membrane and bulk crystallization was induced. According to SEM images and fitting results of Hermia's models, the already-formed bulk crystallization by 1.90 mg/mg TOC KMnO4 could deposit on membranes more easily, followed by the formation of a denser fouling layer. Overall, the present study provided new insights into the design of reliable pre-oxidation strategies for alleviating membrane fouling during nanofiltration of brackish water.

Gravity-driven membrane system treating heavy metals-containing secondary effluent: Improved removal of heavy metals and mechanism.

This study aimed at investigating the removal performance of the gravity-driven membrane (GDM) system in treating the heavy metals-containing secondary effluent, as well as evaluating the respective roles of Fe and Mn addition on the removal of heavy metals. GDM process with the formation of biocake layer exerted effective removals of Cr, Pb and Cd, with an average removal efficiency of 98%, 95% and 40%, respectively, however, after removing the biocake layer, the removal efficiencies of Cr, Pb and Cd reduced to 59%, 85% and 19%, respectively, indicating that the biocake layer played a fundamental role in removing heavy metals. With the assistance of Fe, the removal efficiency of heavy metals increased, and exhibited a positive response to the Fe dosage, due to the adsorption by the freshly generated iron oxides. On the contrary, the Mn involvement would result in the reduction of Cd removal due to the competitive adsorption of residual dissolved Mn2+ and Cd. Furthermore, the addition of a high dosage of Fe increased the diversity of eukaryotic communities and facilitated the elimination of heavy metals, however, the involvement of Mn would lead to a reduction in microbial diversity, resulting in a decrease of heavy metal removal efficiency. These findings are expected to develop new tactics to enhance heavy metal removal and promote widespread application of GDM technology in the fields of deep treatment of heavy metals-containing wastewater and reclamation of secondary effluent.

Employing Visible Light To Construct Photoinitiated Polymerized Nanofiltration Membranes for High Permeation and Environmental Micropollutant Removal.

Improving the nanofiltration (NF) performance of membrane-based treatment is conducive to promoting environmental water recycling and addressing water resource depletion. Combinations of light, electricity, and heat with traditional techniques of preparing membranes should optimize membrane performance. Interfacial polymerization and photopolymerization were integrated to construct a photopolymerized thin-film composite NF membrane with a ridged surface morphology. Under visible light initiation, 2-acrylamido-2-methyl-1-propanesulfonic acid was crosslinked with the polyamide network. The control effects of light on the membrane surface and physicochemical properties were revealed via infrared thermal images and response surface methodology. To present the diffusion motion of piperazine molecules, molecular dynamics simulations were implemented. Through density functional theory simulations, the crosslinking mechanism of the photoinduced NF network was identified and verified. The surface physicochemical characteristics and perm-selectivity performance were systematically illustrated. The photopolymerized membrane outperformed the pristine in permeability and selective separation competence; without degradation of solute repulsion, the water permeation was enhanced to 33.5 L m-2 h-1 bar-1, 6.6 times that of the initial membrane. In addition, the removal of organic contaminants and antifouling capacities were improved. This work represents a novel lead for applying sustainable resources in constructing high-performance membranes for environmental challenges.

Fe, Mn and me.

In over 60 years of research, my team and I have focused on Fe/Mn removal and the application of KMnO4 in drinking water purification, and we have made several technological innovations during this period. In response to the basic need to remove Fe and Mn from groundwater sources in the early days of People's Republic of China, I firstly introduced a catalytic technology involving the application of natural manganese sand produced in China as one of the simplest, cost-effective techniques. During experiments, many phenomena that were inconsistent with conventional theories were observed and a new mechanism was proposed, indicating iron/manganese active films as a catalytic agent instead of MnO2. These films were found to be attached to the surface of natural manganese sand. Fe/Mn-containing compounds with special structures and catalytic features were identified by applying various analytical methods. Drinking water safety was also strengthened by applying KMnO4 as a new cost-effective chemical for source waters facing environmental pollution in China. Experiments showed that KMnO4 can effectively remove many pollutants, including trace organic micro-pollutants, by the combined effects of oxidation and adsorption, which were revealed and confirmed for the first time. Through the application of GC/MS analysis of water samples before and after KMnO4 treatment of samples from various surface water sources, the oxidation by-products from KMnO4 were found to be nontoxic. Therefore, KMnO4 is considered to be a safer chemical in comparison with other conventional oxidants (e.g. HOCl). Previous studies also showed several novel features of KMnO4, such as enhanced coagulation with chlorine, improved algae removal, and increased removal of organically bound manganese. In particular, the combined use of KMnO4 and chlorine could achieve the same disinfection effect at much lower (50%) chlorine dosages. In addition, there are various chemicals and substances that can be combined with KMnO4 to improve decontamination performance. Based on extensive experiments, permanganate compounds were found to be highly efficient in removing heavy metals, e.g., thallium. My research also found that both KMnO4 and powdered activated carbon were highly effective for removing odors and taste. Therefore, we developed a hybrid combination of these two technologies and successfully applied them in many water treatment plants, not only for taste and odor, but also to remove organic micro-pollutants in drinking water. This paper provides a summary of the aforementioned studies that were conducted by me, in collaboration with water treatment industry experts in China, and my graduate students. As a consequence of these studies, several techniques are now widely used in drinking water production in China.

Synergistic effect of potassium ferrate and ferrous iron for improving ultrafiltration performance in algae-laden water treatment.

The application of ultrafiltration (UF) technology in algae-laden water is limited due to the serious membrane fouling caused by algal foulants. Herein, a Ferrate/FeSO4(Fe(VI)/Fe(II)) pretreatment was proposed aiming to improve the performance of UF. The results showed that the synergistic of Fe(VI) and Fe(II) significantly increased the zeta potential of Microcystis aeruginosa, which enhanced the agglomerative tendency of algal foulants, and the particle size of flocs remarkably increased due to the in-situ generated Fe(III). Results from dissolved organic carbon (DOC), UV254, K+, and fluorescent spectra indicated that the introduction of Fe(II) avoided the excessive oxidation of Fe(VI) to algal cells and reduced the production of intracellular organic matter (IOM), while the strong coagulation efficiency of in-situ Fe(III) further enhanced the removal effect of algal organics. Meanwhile, the molecular weight distribution showed that macromolecular organics were decomposed into low molecular matters under Fe(VI) oxidation, while the Fe(VI)/Fe(II) process reduced the formation of small molecular matters compared with single Fe(VI) pretreatment. The algal-source fouling was efficaciously mitigated under the optimal experimental condition, the terminal membrane flux could be increased from 0.16 to 0.62, while reversible and irreversible fouling decreased by 67.1% and 64.1%, respectively. Modeling analysis demonstrated that the Fe(VI)/Fe(II) process altered the fouling mechanism by delaying the formation of cake filtration. Membrane interface characterization further indicated that large size algal flocs form a loose cake layer and reduce the deposition of algal pollutants on the membrane surface. The Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory confirmed that the hydrophobic adsorption between the algal foulant and the membrane was weakened, thus relieving the membrane fouling. Overall, this strategy can be considered for application in improving the UF performance and mitigating algal-source membrane fouling.

Controlling ultrafiltration membrane fouling in surface water treatment via combined pretreatment of O3 and PAC: Mechanism investigation on impacts of technological sequence.

In this research, the effects of combined powdered activated carbon (PAC)-ozone (O3) pretreatment on ultrafiltration (UF) performance were comprehensively examined and compared with the conventional O3-PAC pretreatment. The performance of pretreatments on mitigating membrane fouling caused by Songhua River water (SHR) was evaluated by specific flux, membrane fouling resistance distribution, and membrane fouling index. Moreover, the degradation of natural organic matter in SHR was investigated by UV absorbance at 254 nm (UV254), dissolved organic carbon (DOC), and fluorescent organic matter. Results showed that the 100PAC-5O3 process was the most effective in improving the specific flux, with 82.89 % and 58.17 % reductions in the reversible fouling resistance and irreversible fouling resistance respectively. Additionally, the irreversible membrane fouling index was reduced by 20 % relative to 5O3-100PAC. The PAC-O3 process also exhibited superior performance in the degradation of UV254, DOC, three fluorescent components, and three micropollutants in the SHR system compared to O3-PAC pretreatment. The O3 stage played a major role in mitigating membrane fouling, while PAC pretreatment enhanced the oxidation in the subsequent O3 stage during the PAC-O3 process. Furthermore, the Extended Derjaguin-Landau-Verwey-Overbeek theory and pore blocking-cake layer filtration model fitting analysis were employed to explain the mechanisms of membrane fouling mitigation and fouling patterns transformation. It was found that PAC-O3 significantly increased the repulsive interactions between the foulants and the membrane, which restrained the formation of the cake layer filtration stage. Overall, this study evidenced the potential of PAC-O3 pretreatment in surface water treatment applications, providing new insights into the mechanism of controlling membrane fouling and improving the permeate quality.

Fe(II)-Modulated Microporous Electrocatalytic Membranes for Organic Microcontaminant Oxidation and Fouling Control: Mechanisms of Regulating Electron Transport toward Enhanced Reactive Oxygen Species Activation.

Regulation of the fast electron transport process for the generation and utilization of reactive oxygen species (ROS) by achieving fortified electron "nanofluidics" is effective for electrocatalytic oxidation of organic microcontaminants. However, limited available active sites and sluggish mass transfer impede oxidation efficiency. Herein, we fabricated a conductive electrocatalytic membrane decorated with hierarchical porous vertically aligned Fe(II)-modulated FeCo layered double hydroxide nanosheets (Fe(II)-FeCo LDHs) in an electro-Fenton system to maximize exposure of active sites and expedite mass transfer. The nanospaced interlayers of Fe(II)-FeCo LDHs within the microconfined porous structure formed by its vertical nanosheets highly boost the micro/nanofluidic distribution of target pollutants to active centers/species, achieving accelerated mass transferability. Aliovalent substitution by Fe(II) activates in-plane metallics to maximize the available active sites and makes each Fe(II)-FeCo LDH nanosheet a geometrical nanocarrier for constructing a fast electron "nanofluidic" to accelerate Fe(II) regeneration in Fe(III)/Fe(II) cycles. As a result, the Fe(II)-FeCo LDHs exhibited improved reactivity in catalyzing H2O2 to •OH and 1O2. Accordingly, the membrane exhibited a higher atrazine degradation kinetic (0.0441 min-1) and degradation rate (93.2%), which were 4.7 and 2.1 times more than those of the bare carbon nanotube membrane, respectively. Additionally, the enhanced hydrophilic and strongly oxidized reactivity synergistically mitigated the organic fouling occurring in the pores and surface of the membrane. These findings clarify the activation mechanism of ROS over an innovative electrocatalytic membrane reactor design for organic microcontaminant treatment.

Municipal wastewater contains antibiotic treatment using O2 transfer membrane based biofilm reactor: Interaction between regular pollutants metabolism and sulfamethoxazole degradation.

The antibiotic sulfamethoxazole (SMX) is frequently detected in wastewater treatment plant effluents and has attracted significant attention owing to its significant potential environmental effects. We present a novel O2 transfer membrane based biofilm reactor (O2TM-BR) to treat municipal wastewater to eliminate containing SMX. Furthermore, conducting metagenomics analyses, the interactions in biodegradation process between SMX and regular pollutants (NH4+-N and COD) were studied. Results suggest that O2TM-BR yields evident advantages in SMX degradation. Increasing SMX concentrations did not affect the efficiency of the system, and the effluent concentration remained consistent at approximately 17.0 µg/L. The interaction experiment showed that heterotrophic bacteria tend to consume easily degradable COD for metabolism, resulting in a delay (>36 h) in complete SMX degradation, which is 3-times longer than without COD. It is worth noting that the taxonomic and functional structure and composition in nitrogen metabolism were significantly shifted upon the SMX. NH4+-N removal remained unaffected by SMX in O2TM-BR, and the expression of K10944 and K10535 has no significant difference under the stress of SMX (P > 0.02). However, the K00376 and K02567 required in the nitrate reductase is inhibited by SMX (P < 0.01), which hinders the reduction of NO3--N and hence the accumulation of TN. This study provides a new method for SMX treatment and reveals the interaction between SMX and conventional pollutants in O2TM-BR as well as the microbial community function and assembly mechanism.