Constructing hollow core-shell Z-scheme heterojunction CdS@CoTiO3 nanorods for enhancing the photocatalytic degradation of 2,4-DCP and TC.

Constructing Z-scheme heterojunctions incorporating an exquisite hollow structure is an effective performance regulation strategy for the realization of high quantum efficiency and a strong redox ability over photocatalysts. Herein, we report the delicate design and preparation of a core-shell hollow CdS@CoTiO3 Z-scheme heterojunction with a CdS nanoparticle (NP)-constructed outer shell supported on a CoTiO3 nanorod (NR) inner shell. The in situ growth synthetic method led to a tightly connected interface for the heterojunction between CdS and CoTiO3, which shortened the transport distance of photoinduced charges from the interface to the surface. The promoted charge carrier separation efficiency and the retained strong redox capacity caused by the Z-scheme photoinduced charge-transfer mechanism were mainly responsible for the boosted photocatalytic performance. Additionally, the well-designed core-shell structure afforded a larger interfacial area by the multiple direction contact between CdS and CoTiO3, ensuring sufficient channels for efficient charge transfer, and thus further boosting the photocatalytic activity. As an efficient photocatalyst, the optimized CdS@CoTiO3 nanohybrids displayed excellent 2,4-dichlorophenol (2,4-DCP) and tetracycline (TC) degradation efficiencies of 91.3% and 91.8%, respectively. This study presents a Z-scheme heterojunction based on ecofriendly CoTiO3, which could be valuable for the development of metal perovskite photocatalysts for application in environmental remediation, and also demonstrated the tremendous potential of integrating a Z-scheme heterojunction with the morphology design of photocatalyts.

Ecotoxicity and resistance genes induction changing of antibiotic tetracycline degradation products dominated by differential free radicals.

Studying the ecological risks of antibiotics and their degradation products is of great importance to water environment security and advanced oxidation processes (AOPs) development. This work studied the changes and internal influencing mechanisms of ecotoxicity and the capacity for inducing antibiotic resistance genes (ARGs) shown by the tetracycline (TC) degradation products generated in AOPs with differential free radicals. Under the action of superoxide radicals and singlet oxygen in the ozone system, and sulfate and hydroxyl radicals in the thermally activated potassium persulfate system, TC exhibited differential degradation pathways and resulted in the differential growth inhibition trends on the determined strains. Microcosm experiments combined with metagenomics were also performed to analyze the remarkable changes in the TC resistance genes tetA (60), tetT, and otr(B) induced by the degradation products and ARG hosts in the natural water environment. Microcosm experiments exhibited that the microbial community in actual water have changed significantly with the addition of TC and degradation intermediates. Furthermore, the richness of genes related to oxidative stress was investigated to discuss the effect on reactive oxygen species production and SOS response caused by TC and its intermediates.

Advances and challenges in the removal of organic pollutants via sulfate radical-based advanced oxidation processes by Fe-based metal-organic frameworks: A review.

Organic contaminants, notorious for their complexity and resistance to degradation, are prevalent in aquatic environments, posing severe threats to ecosystems. Sulfate radical-based advanced oxidation processes (SR-AOPs), known for their stability and high effectiveness, have become a common choice for treating organic wastewater. Metal-organic framework materials (MOFs) have garnered substantial attention due to their facile chemical manipulation, unique structural configurations, and other favorable properties. Therefore, this article critically reviews recent advances in research involving the utilization of Fe-based MOFs (Fe-MOFs) and their derivatives in SR-AOPs. Specifically, it highlights the manipulation of influencing factors within the system to enhance the degradation of organic pollutants. The mechanisms and applications underlying the degradation of organic pollutants in the SR-AOPs system are also elucidated.

Mechanism of biochar composite (BN3Z0.5BC) activated peracetic acid for efficient antibiotic degradation: Synergistic effect between free radicals and non-free radicals.

This study utilized corn straw as the feedstock to synthesize biochar (BC) loaded with cobalt-zeolitic imidazolate framework nanoparticles and boron nitride quantum dots. The prepared BC composite, named BN3Z0.5BC, efficiently activated peracetic acid (PAA), resulting in the degradation of 94.8% of sulfadiazine (SDZ) in five minutes. Compared to pure BC, the SDZ removal rate increased nearly 5-fold. Mechanism analysis revealed that the main degradation pathway involves synergism between free and non-free radicals. The defect structure on the BC surface possesses a high charge density, stimulating PAA to produce more active species, while nitrogen-oxygen vacancy formation significantly promotes charge transfer. Besides, the unique structure of BC ensures good stability and recyclability, effectively controlling metal leaching. The BN3Z0.5BC/PAA system shows promising applicability across various water matrices, indicating a favorable application outlook.

Dissecting the ecological risks of sulfadiazine degradation intermediates under different advanced oxidation systems: From toxicity to the fate of antibiotic resistance genes.

The incomplete degradation of antibiotics in water can produce intermediates that carry environmental risks and thus warrant concerns. In this study, the degradation of high concentrations of antibiotic sulfadiazine (SDZ) by advanced oxidation processes that leverage different reactive oxide species was systematically evaluated in terms of the influence of different degradation intermediates on the propagation of antibiotic resistance genes (ARGs). The ozone, persulfate, and photocatalytic oxidation systems for SDZ degradation are dominated by ozone, direct electron transfer, and singlet oxygen, hole, and superoxide radicals, respectively. These processes produce 15 intermediates via six degradation pathways. Notably, it was determined that three specific intermediates produced by the ozone and persulfate systems were more toxic than SDZ. In contrast, the photocatalytic system did not produce any intermediates with toxicity exceeding that of SDZ. Microcosm experiments combined with metagenomics confirmed significant changes in microbiota community structure after treatment with SDZ and its intermediates, including significant changes in the abundance of Flavobacterium, Dungenella, Archangium, and Comamonas. This treatment also led to the emergence of sulfonamide ARGs. The total abundance of sulfonamide ARGs was found to be positively correlated with residual SDZ concentration, with the lowest total abundance observed in the photocatalytic system. Additionally, the correlation analysis unveiled microbiota carrying sulfonamide ARGs.

Oxidation effects on Microcystis aeruginosa inactivation through various reactive oxygen species: Degradation efficiency, mechanisms, and physiological properties.

The study investigated the inactivation of Microcystis aeruginosa using a combined approach involving thermally activated peroxyacetic acid (Heat/PAA) and thermally activated persulfate (Heat/PDS). The Heat/PDS algal inactivation process conforms to first-order reaction kinetics. Both hydroxyl radical (•OH) and sulfate radical (SO4-•) significantly impact the disruption of cell integrity, with SO4-• assuming a predominant role. PAA appears to activate organic radicals (RO•), hydroxyl (•OH), and a minimal amount of singlet oxygen (1O2). A thorough analysis underscores persulfate's superior ability to disrupt algal cell membranes. Additionally, SO4-• can convert small-molecule proteins into aromatic hydrocarbons, accelerating cell lysis. PAA can accelerate cell death by diffusing into the cell membrane and triggering advanced oxidative reactions within the cell. This study validates the effectiveness of the thermally activated persulfate process and the thermally activated peroxyacetic acid as strategies for algae inactivation.

Recent advances in electrospinning-nanofiber materials used in advanced oxidation processes for pollutant degradation.

Electrospun nanofiber membranes have emerged as a novel catalyst, demonstrating exceptional efficacy in advanced oxidation processes (AOPs) for the degradation of organic pollutants. Their superior performance can be attributed to their substantial specific surface area, high porosity, ease of modification, rapid recovery, and unparalleled chemical stability. This paper aims to comprehensively explore the progressive applications and underlying mechanisms of electrospun nanofibers in AOPs, which include Fenton-like processes, photocatalysis, catalytic ozonation, and persulfate oxidation. A detailed discussion on the mechanism and efficiency of the catalytic process, which is influenced by the primary components of the electrospun catalyst, is presented. Additionally, the paper examines how concentration, viscosity, and molecular weight affect the characteristics of the spinning materials and seeks to provide a thorough understanding of electrospinning technology to enhance water treatment methods. The review proposes that electrospun nanofiber membranes hold significant potential for enhancing water treatment processes using advanced oxidation methods. This is attributed to their advantageous properties and the tunable nature of the electrospinning process, paving the way for advancements in water treatment through AOPs.

Antibiotic sulfadiazine degradation by persulfate oxidation: Intermediates dependence of ecotoxicity and the induction of antibiotic resistance genes.

To preserve the water resources, this study has analyzed the ecotoxicity and antibiotic resistance genes (ARGs) induction capacity of sulfadiazine degradation intermediates resulting from persulfate activation oxidation enhanced by ultraviolet, ultrasound and microwave. The five degradation pathways caused by the contribution discrepancy of electron transfer and singlet oxygen (1O2) and variations in the ecotoxicity of different degradation products were analyzed. Microcosm experiment exhibited that the microbial community in actual water changed significantly with SDZ and degradation intermediates, in which the dominant genera were Aeromonas, Cupriavidus, Elizabethkingia and Achromobacter. Except for the selective pressure on bacteria, the degradation intermediates also exert a certain degree or even stronger induction on sulfonamide ARGs (sul4, sul1 and sul2) than SDZ. Furthermore, the potential hosts for sulfonamide ARGs were revealed by network analysis. These results provide a better understanding of antibiotics degradation mechanism and ARGs occurrence, which is useful for controlling the spread of ARGs.

Biochar loaded with CoFe2O4 enhances the formation of high-valent Fe(IV) and Co(IV) and oxygen vacancy in the peracetic acid activation system for enhanced antibiotic degradation.

Corn straw and sludge-derived biochar composite (BC) loaded with CoFe2O4 was successfully prepared to activate peracetic acid (PAA) for efficient degradation of tetracycline hydrochloride (TCH). Within 60 s, 96 % TCH removal efficiency was achieved through a non-free radical degradation pathway, primarily driven by singlet oxygen (1O2). The mechanism involves the electron-rich groups on the biochar surface, which facilitate the cleavage of the PAA OO bond to generate •O2-/1O2 and provide electrons to induce the formation of high-valent Fe(IV) and Co(IV). The oxygen vacancies on the surface of the CoFe2O4-loaded biochar composite (CFB-2) contribute partially to 1O2 production through their transformation into a metastable intermediate with dissolved oxygen. Moreover, elevated temperatures further enhance PAA activation by CFB-2, leading to increased reactive oxygen species (ROS) production through PAA decomposition, thereby promoting TCH removal. This study offers new insights into the catalysis of metal-loaded biochar for efficient TCH degradation via non-free radical generation.

Recent advances in biodegradation of emerging contaminants - microplastics (MPs): Feasibility, mechanism, and future prospects.

Plastics have become an essential part of life. When it enters the environment, it migrates and breaks down to form smaller size fragments, which are called microplastics (MPs). Compared with plastics, MPs are detrimental to the environment and pose a severe threat to human health. Bioremediation is being recognized as the most environmentally friendly and cost-effective degradation technology for MPs, but knowledge about the biodegradation of MPs is limited. This review explores the various sources of MPs and their migration behavior in terrestrial and aquatic environments. Among the existing MPs removal technologies, biodegradation is considered to be the best removal strategy to alleviate MPs pollution. The biodegradation potential of MPs by bacteria, fungi and algae is discussed. Biodegradation mechanisms such as colonization, fragmentation, assimilation, and mineralization are presented. The effects of MPs characteristics, microbial activity, environmental factors and chemical reagents on biodegradation are analyzed. The susceptibility of microorganisms to MPs toxicity might lead to decreased degradation efficiency, which is also elaborated. The prospects and challenges of biodegradation technologies are discussed. Eliminating prospective bottlenecks is necessary to achieve large-scale bioremediation of MPs-polluted environment. This review provides a comprehensive summary of the biodegradability of MPs, which is crucial for the prudent management of plastic waste.

Synergistic defect and doping engineering building strong bonded S-scheme heterojunction for photocatalysis.

Photocatalytic degradation of pollutants is considered a promising approach for wastewater treatment, but is hampered by low efficiency and limited understanding of degradation pathways. A novel oxygen-doped porous g-C3N4/oxygen vacancies-rich BiOCl (OCN/OVBOC) heterostructure was prepared for photocatalytic degradation of bisphenol A (BPA). The synergistic defect and doping engineering favor the formation of strong bonded interface for S-scheme mechanism. Among them, 0.3 OCN/OVBOC showed the most excellent degradation rate, which was 8 times and 4 times higher than that of pure g-C3N4 and BiOCl, respectively. This excellent performance is mainly attributed to the significantly enhanced charge separation via strong bonded interface and redox capability of the S-scheme heterojunction structure, by tuning the coordination excitation and electron localization of the catalyst via O doping and vacancies. This work provides important insights into the role of synergistic defect and doping engineering in facilitating the formation of strong bonded S-scheme heterojunction and ultimately sheds new light on the design of efficient photocatalysts.

Antibiotics degradation by advanced oxidation process (AOPs): Recent advances in ecotoxicity and antibiotic-resistance genes induction of degradation products.

Antibiotic contamination could cause serious risks of ecotoxicity and resistance gene induction. Advanced oxidation processes (AOPs) such as Fenton, photocatalysis, activated persulfate, electrochemistry and other AOPs technologies have been proven effective in the degradation of high-risk, refractory organic pollutants such as antibiotics. However, due to the limited mineralization ability, a large number of degradation intermediates will be produced in the oxidation process. The residual or undiscovered ecological risks of degradation products are potential safety hazards and problems necessitating comprehensive studies. In-depth investigations especially on the full assessments of ecotoxicity and resistance genes induction capability of antibiotic degradation products are important issues in reducing the environmental problems of antibiotics. Therefore, this review presents an overview of the current knowledge on the efficiency of different AOPs systems in reducing antibiotics toxicity and antibiotic resistance.

Responses of gut microbiomes to commercial polyester polymer biodegradation in Tenebrio molitor Larvae.

Polyethylene terephthalate (PET) is a mass-produced fossil-based plastic polymer that contributes to catastrophic levels of plastic pollution. Here we demonstrated that Tenebrio molitor (mealworms) was capable of rapidly biodegrading two commercial PET resins (microplastics) with respective weight-average molecular weight (Mw) of 39.33 and 29.43 kDa and crystallinity of 22.8 ± 3.06% and 18 ± 2.25%, resulting in an average mass reduction of 71.03% and 73.28% after passage of their digestive tract, and respective decrease by 9.22% and 11.36% in Mw of residual PET polymer in egested frass. Sequencing of 16 S rRNA gene amplicons of gut microbial communities showed that dominant bacterial genera were enriched and associated with PET degradation. Also, PICRUSt prediction exhibited that oxidases (monooxygenases and dioxygenases), hydrolases (cutinase, carboxylesterase and chitinase), and PET metabolic enzymes, and chemotaxis related functions were up-regulated in the PET-fed larvae. Additionally, metabolite analyses revealed that PET uptake caused alterations of stress response and plastic degradation related pathways, and lipid metabolism pathways in the T. molitor larvae could be reprogrammed when the larvae fed on PET. This study provides new insights into gut microbial community adaptation to PET diet under nutritional stress (especially nitrogen deficiency) and its contribution to PET degradation.

High microwave responsivity Co-Bi25FeO40 in synergistic activation of peroxydisulfate for high efficiency pollutants degradation and disinfection: Mechanism of enhanced electron transfer.

Cobalt doped Bi25FeO40 was used as a heterogeneous catalyst in microwave (MW) co-activation of peroxydisulfate (PDS) system for organic contaminant purification and disinfection simultaneously. Due to low charge-transfer resistance and fast electron migration, Co-Bi25FeO40 showed superior catalytic efficiencies for activation PDS to degrade over 92.0% of bisphenol A (BPA) with the initial concentrations ranging from 40 mg/L to 120 mg/L in 5.0 min. The non-radical oxidation pathway via electron transfer regime on the surface of Co-Bi25FeO40 was the dominant reactive species in the reaction system. Benefit from the energy transfer and cross-coupling reactions of microwave, the Co-Bi25FeO40/MW/PDS system can generate abundant reactive sites to facilitate the formation of more surface-bonding complexes. Microwave energy can be absorbed by Co-Bi25FeO40 catalysts to promote activation of PDS and production of nanobubbles. The generated nanobubbles increase the temperature of the local solution to promote the reaction. The Co-Bi25FeO40/MW/PDS system also exhibited excellent bactericidal capability for Escherichia coli (E.coli). The catalysts, oxidants and microwaves acted on E. coli to form physical, and oxidative pressure simultaneously, causing cell damaged and made bacterial death. This work provides prospects toward high-efficiency integration of contaminant purification and pathogenic microorganisms inactivation.

Porous Oxygen-Doped g-C3N4 with the Different Precursors for Excellent Photocatalytic Activities under Visible Light.

Antibiotic contamination has received widespread attention globally. In this work, the oxygen-doped porous graphite carbonitride (g-C3N4) was prepared with urea and ammonium oxalate (CNUC) or urea and glycine (CNUG) as precursors by thermal polymerization. Using bisphenol A (BPA) as a probe and CNUC or CNUG as photocatalysts, the removal performance test was carried out. Meanwhile, all prepared photocatalysts were characterized by XRD, FT-IR, SEM, TEM, XPS, UV-Vis DRS, PL and EIS. Under visible light irradiation, both CNUC and CNUG exhibited about seven and five times greater photocatalytic activity than that of pure g-C3N4, respectively. The radical capture experiments verified that superoxide radicals (•O2-) and holes (h+) were the main active species in the photocatalytic degradation of BPA by CNUC, and the possible photocatalytic mechanism of CNUC was proposed. In addition, all these results indicate that CNUC catalyst can effectually inhibit the photocorrosion and keep superior stability. The proposed technique provides a prospective approach to develop nonmetal-modified photocatalysts for future applications.

Introduction of oxygen vacancy to manganese ferrite by Co substitution for enhanced peracetic acid activation and 1O2 dominated tetracycline hydrochloride degradation under microwave irradiation.

High microwave-response cobalt-substituted manganese ferrite (CMFO-0.5) was successfully synthesized as a heterogeneous catalyst for efficient peracetic acid (PAA) activation and tetracycline hydrochloride (TCH) degradation with singlet oxygen (1O2) as the dominated reactive oxidized species (ROS). The removal efficiency of TCH could reach 98.16% within 6 min under microwave irradiation when the CMFO-0.5 was added at 20 mg/L. It's found that the Co substitution could produce the oxygen vacancies (OVs), improve the microwave (MW) absorbing performance and enhance the internal electron transfer efficiency of materials. The phenomenon why 1O2 as the dominated ROS rather than hydroxyl radical (•OH) and organic radicals (R-O•) would be explained by the following aspects: the oxygen adsorbed on the OVs can accept the electron transformed from PAA to form superoxide radical (•O2-), which will disproportionate to form 1O2; the energy generated by the non-thermal effect of MW can dissociate PAA to generate peroxy-group for 1O2 generation. Furthermore, the possible TCH degradation pathways were proposed based on DFT theory calculations and product identification, and the toxicity predictions of the degradation products were also performed by the Ecological Structure-Activity Relationship Model (ECOSAR) software. Additionally, the decrease of acute toxicity of treated TCH, excellent stability and strong resistance towards water matrix fully demonstrate the superiority of the proposed system for practical application in wastewater treatment.

Lutein production by microalgae using corn starch wastewater pretreated with rapid enzymatic hydrolysis.

The main purpose of this study was to explore the pretreatment process of corn starch wastewater (CSW) and engineered microalgae cultivation strategy to improve the nutrient recovery from wastewater and the yield of microalgae lutein. One-stage enzymatic hydrolysis utilizing α-amylase and glucoamylase simultaneously was established to efficiently harvest a maximum concentration of reducing sugar content of 7.26 g/L from CSW in 50 min. Lutein yield of 10.96 mg/L was obtained under 24 h continuous illumination with 2200 Lux light intensity. Furthermore, a cyclic feeding cultivation strategy was developed to improve lutein accumulation and COD removal up to 25.9 mg/L and 50.7%, respectively, after three cultivation cycles. Lutein yield of 14.86 mg/L and COD removal efficiency of 73.2% was achieved with further implementation in actual wastewater. This work provided a new perspective in developing the potential of cultivating microalgae with corn starch wastewater to produce high-value lutein.

Advanced oxidation process based on hydroxyl and sulfate radicals to degrade refractory organic pollutants in landfill leachate.

As a special type of wastewater produced in the landfill, leachate is mainly composed of organic pollutants, inorganic salts, ammonia nitrogen and heavy metals, and featured by high pollutants concentration, complex composition and large fluctuations in water quality and volume. Biological, chemical and physical methods have been proposed to treat landfill leachate, but much attention has been paid to the advanced oxidation processes (AOPs), due to their high adaptability and organic degradation efficiency. This paper summarizes the recent findings on the AOPs based on hydroxyl radical (OH) (e.g., ozonation and catalyzed ozone oxidations, Fenton and Fenton-like oxidations) and sulfate radical (SO4-) (e.g., activated and catalyzed persulfate oxidations), especially the production routes of free radicals and mechanisms of action. When dealing with some special landfill leachates, it is difficult for a single advanced oxidation technology to achieve the expected results, but the synergistic combination with biological or physical methods can produce satisfactory outcomes. Therefore, this paper has summarized the application of these combined treatment technologies on landfill leachate.

Inhibition of biofouling in membrane bioreactor by metabolic uncoupler based on controlling microorganisms accumulation and quorum sensing signals secretion.

Biofouling is a limiting bottleneck in the development of membrane bioreactor (MBR) since the birth of this technology. Recently, the biofouling control strategy based on interfering with the bacterial quorum sensing (QS) system is highly desirable for biofouling control in MBR. In this study, three lab-scale parallel MBR systems were operated over 100 days to investigate the inhibitory effect of a metabolic uncoupler (3,3',4',5-tetrachlorosalicylanilide, TCS) on biofouling and the potential mechanism for biofouling control. Compared to the control MBR, the fouling cycle duration of MBR 2 with 100 µg/L TCS extended over two times. The attached biomass on membrane in MBR 2 decreased over 50% at the end of each operating period, which indicated that the addition of TCS significantly mitigated microorganisms accumulation on membrane. The content of interspecies QS signal (autoinducer-2) and intraspecific QS signals (N-octanoyl-dl-homoserine lactone, C8-HSL) was reduced by the TCS, suggesting the secretion of QS signals in MBR were affected by uncoupler. Although the addition of TCS induced brief fluctuations of extracellular proteins and polysaccharides, microorganisms seemed to rapidly acclimatize to the presence of TCS and then the secretion of extracellular polymeric substances (EPS) was inhibited by 100 µg/L TCS. The continuous operation of MBR was not be affected by the low-concentration uncoupler via the analysis of substrate removal and sludge growth. This study systematically evaluated the effect and inhibitory efficiency of TCS on biofouling, biomass accumulation, QS signals, EPS and treatment performances, demonstrating the feasibility of metabolic uncoupler for biofouling control in MBR.

Hydroxyl radical dominated degradation of aquatic sulfamethoxazole by Fe0/bisulfite/O2: Kinetics, mechanisms, and pathways.

In this study, batch experiments were carried out to investigate the key factors on sulfamethoxazole (SMX) removal kinetics in a new AOPs based on the combination of zero valent iron (Fe0) and bisulfite (S(IV)). With the increase of Fe0 from 0.25 mM to 5 mM, the removal rate of SMX was linearly increased in the Fe0/S(IV)/O2 system by accelerating the activation of S(IV) and Fe0 corrosion to accelerate. In the first 10 min of reaction, the increasing concentration of S(IV) inhibited SMX removal after since the high S(IV) concentration quenched reactive oxidative species (ROS). Then SMX removal rate was accelerated with the increase of S(IV) concentration after S(IV) were consumed up. The optimal ratio of S(IV) concentrations to Fe0 concentration for SMX removal in the Fe0/S(IV)/O2 system was 1:1. With SMX concentrations increasing from 1 to 50 µM, SMX removal rate was inhibited for the limitation of ROS yields. Although the presence of SO4- and OH was confirmed by electron paramagnetic resonance (EPR) spectrum, OH was identified as the dominant ROS in the Fe0/S(IV)/O2 system by chemical quenching experiments. Besides, strong inhibitive effects of 1,10-phenanthroline on SMX degradation kinetics by Fe0/S(IV)/O2 proved that the generation of ROS was rely on the release of Fe(II) and Fe(III). The generation of SO4- was ascribed to the activation of S(IV) by Fe(II)/Fe(III) recycling and the activation of HSO5- by Fe(II). And OH was simultaneously transformed from SO4- and generated by Fe0/O2. Density functional theory (DFT) calculation was conducted to reveal special reactive sites on SMX for radicals attacking and predicted intermediates. Finally, four possible SMX degradation pathways were accordingly proposed in the Fe0/S(IV)/O2 system based on experimental methods and DFT calculation.