Ecological Structure Activity Relationships Research Articles

Insights into the Removal of Organic Contaminants by Co-CeO2 Nanocatalysts via CaCO3 Activation: Performance, Kinetic, and Mechanism.

The advanced oxidation process based on S(IV) has garnered increasing attention, owing to its efficiency in degrading contaminants. Here, a cobalt-doped cerium oxide catalyst (Co-CeO2) was employed to activate calcium sulfite (CaSO3) for imidacloprid degradation. The Co-CeO2 catalyst was characterized by using SEM, BET, XRD, and XPS techniques to analyze its structural and chemical properties. XPS analysis revealed the presence of Co0, Co2+, and Co3+ species in the Co-CeO2 catalyst. Compared to the CeO2/CaSO3 system, the Co-CeO2/CaSO3 system significantly enhanced the degradation rate of imidacloprid from 5.00% to 94.01%. Scavenging experiments, in conjunction with electron paramagnetic resonance spectroscopy, identified hydroxyl radicals (•OH), sulfate radicals (SO4•-), superoxide radicals (O2•-), sulfite radicals (SO3•-), and singlet oxygen (1O2) as the primary reactive species responsible for the degradation of imidacloprid within the Co-CeO2/CaSO3 system. Density functional theory calculation analysis was employed to investigate the specific sites of imidacloprid attacked by reactive oxygen species, proposing four potential degradation pathways. Furthermore, the Ecological Structure Activity Relationships (ECOSAR) program predicted a significant diminution in the toxicity of intermediate products compared to imidacloprid. Even after five cycles, Co-CeO2 maintained an excellent removal efficiency of 86.35%.

The design and preparation of PDI modified NH2-MIL-101(Fe) for high efficiency removal of dimethoate in peroxymonosulfate system: Performance, mechanism, pathway and toxicity assessment

The widespread use of organophosphorus pesticide dimethoate (DMT) in agriculture poses a threat to human health. In this work, the perylene tetracarboxylic diimide (PDI) modified NH2-MIL-101(Fe) (PDI/MIL) with strong covalent bond C(=O)–N were designed and prepared by a step solvothermal method. The synergistic effect between photocatalytic and peroxymonosulfate (PMS) activation for the DMT elimination over PDI/MIL was gained. Interestingly, PDI/MIL(1:10)/PMS showed boosting degradation efficiency (95.6%) for DMT under 18 min simulated sunlight irradiation. Its apparent reaction rate constant was 24.7 times higher than that of NH2-MIL-101(Fe)/PMS. Moreover, its reusability, stability and mineralization ability were evaluated, and a remarkable mineralization rate of 95.3% with 90 min was achieved. The enhanced activity were attributed to the formation of amide bond that exhibited superior charger transport ability and amount of produced active species. Combined the results obtained from the HPLC-MS and molecular structure characteristics of DMT analyzed by Fukui index, the degradation pathways were proposed. The toxicity of intermediates were predicted by Ecological Structure Activity Relationship (ECOSAR), Toxicity Estimation Software Tool (T.E.S.T.), and Vibrio fischeri experiments. Our work provided deep insights into the mechanisms of DMT degradation via photocatalysis-activated PMS over organic semiconductor modified metal organic frameworks.

In-situ electrogenerated persulfate activated by co-existing Cu(II) for sustainable removal of sulfonamides from environmental waters

In this study, in-situ electrogenerated persulfate (E-PS) was proposed as an alternative to the conventional addition of persulfate for advanced oxidation processes (AOPs) with facilitating conversion of co-existing Cu(II) to Cu(I) to degrade antibiotics without requiring any external supply of chemical additives. The degradation rate of sulfamethoxazole (SMX) by E/Cu(Ⅱ)/Na2SO4 system (C0(Cu(Ⅱ))=1mM, C0(Na2SO4)=1mM, E=25V) was 93.3% at t=90min. Quenching combined with electron paramagnetic resonance (EPR) tests revealed that SO4•-, •OH and Cu(Ⅲ) were the primary contributors to SMX degradation. Solution pH, co-existing anions and organic matter affected the degradation performance of SMX. Four degradation pathways were proposed based on transformed products (TPs) determination, with pathways I and II being the dominant ones involving the cleavage of S-N bond in SMX. Ecological structure activity relationships (ECOSAR) program analysis implied that the TPs exhibited lower toxicity levels toward aquatic organisms compared to that of SMX. Additionally, the E/Cu(II)/Na2SO4 system achieved decomposition rates over 80% for various sulfonamides (SAs) and also demonstrated remarkable efficacy for SMX removal in different real waters, including tap water, lake water, river water and aquaculture wastewater, with all exceeding 80% at t=90min. E/Cu(Ⅱ)/Na2SO4 system developed in this study had the potential to be a prospective technique for SAs purification due to its outstanding performance in degrading and detoxifying SAs.

Concentrated solar energy-driven photothermal efficient degradation and mineralization of fluoroquinolone antibiotics in various water bodies

Sunlight-driven advanced oxidation process has promising applications and is increasingly receiving attention for the removal of emerging pollutants. This study describes a concentrated solar energy-driven photothermal (CSEP) system for the efficient degradation of fluoroquinolone antibiotics in wastewater. The operation of concentrating light degradation was not only a simple combination of thermal degradation and sunlight degradation, but the complex photothermal synergies that occurred to achieve degrading fluoroquinolones (FQs) more thoroughly. In the degradation processes, singlet oxygen (1O2), superoxide anion (O2·−), and hydroxyl radical (·OH) play pivotal roles. Additionally, the CSEP system exhibits outstanding defluorination capability (e.g., achieving 100 % defluorination for ciprofloxacin (CIP)). The photodegradation pathways of CIP were investigated using liquid chromatography/tandem mass spectrometry (LC/MS/MS), ion chromatography (IC) analysis, and density functional theory (DFT). Additionally, the aquatic ecological toxicity of CIP was assessed through ecological structure–activity relationship (ECOSAR) modeling and antimicrobial activity testing. Furthermore, this system demonstrates strong adaptability in addressing various natural water bodies, achieving an average degradation rate of over 98.00 % within a short time (3 min, 2 mg·L−1 CIP). In addition, it enhances the potential for synergistic removal of algae and degradation of FQs in complex water ecosystems. The adoption of this CSEP system holds considerable promise in furnishing robust technical support for the treatment and removal of FQs in water and wastewater.

Degradation mechanism and toxicity assessment of clofibric acid by Fe2+/PS process in saline pharmaceutical wastewater

ABSTRACT A considerable effort has been made to exploring the oxidation of clofibric acid (CA) in advanced oxidation processes (AOPs). However, few studies are available on degradation mechanism and toxicity assessment of CA in saline pharmaceutical wastewater. Here the effect of chlorine on the degradation kinetics of CA by Fe2+/ persulfate (PS) process were studied. Oxidation efficiency, mineralisation, intermediate by-products, reactive oxygen species (ROS) and toxicity assessment were examined. Notably, a high removal efficiency (70.91%) but low mineralisation (20.99%) of CA were observed at pH 3.0 during the Fe2+/PS system. Furthermore, we found Cl− exerted a beneficial impact on CA degradation. However, the degree of CA mineralisation was relatively minor. Under high salinity (100 mM) condition, the primary reactive species within the Fe2+/PS system were SO 4 ⋅ − , OH·, Cl2/HClO, and Fe(IV). Several undesirable chlorinated by-products were formed. A reasonable degradation pathway was proposed. According to the ecological structure–activity relationship (ECOSAR) programme, some transformation products exhibited higher toxicity levels than CA itself in both acute and chronic toxicity assessment, especially in high-salinity environments. These findings elucidate an increased challenges and ecological risk for CA oxidation by Fe2+/PS treatment in saline pharmaceutical wastewater.

Electrochemical degradation of aromatic organophosphate esters: Mechanisms, toxicity changes, and ecological risk assessment

Aromatic organophosphate esters (AOPEs), including triphenyl phosphate (TPHP), tricresyl phosphate (TCP), and 2-ethylhexyl diphenyl phosphate (EHDPP), pose significant health and ecological risks. Electrochemical advanced oxidation process (EAOP) is effective in removing refractory pollutants. In this study, the degradation performance and detoxication ability of AOPEs by EAOP were investigated. Hydroxylation, oxidation, and bond cleavage products were identified as major degradation products (DPs) due to the reaction with ·OH and O₂·-. Toxicity assessments using ecological structure activity relationship (ECOSAR) model and flow cytometry (FCM) revealed the cytotoxicity and aquatic toxicity for DPs were significantly decreased. 16S rRNA gene sequencing of sediment exposure to AOPEs and DPs were applied to assess ecological toxicity, and results showed reduced bacterial richness and diversity with EHDPP and TCP, while TPHP slightly enhanced richness. AOPEs and DPs altered bacterial genera involved in carbon, nitrogen, sulfur cycling and organic compound degradation. Bacterial community assembly suggested elevated stochastic processes and reduced ecotoxicity, confirming AOPEs can be effectively detoxified by 10-min EAOP treatment. Molecular ecological network analysis indicated increased complexity and stability of bacterial communities with DPs. These findings comprehensively revealed the toxicity of AOPEs and their DPs and provided the first evidence of effective degradation and detoxification by EAOP from ecotoxicological perspective.

Sonophotocatalytic degradation of rhodamine B dye using Zr doped ZnO nanoparticles: Kinetic study and toxicity assessment

This study investigates sonophotocatalysis for the oxidation of Rhodamine B (RhB) dye using Zr doped ZnO nanoparticles. The synthesized nanoparticles were characterized by scanning electron microscope, Fourier-transform infrared, X-ray diffraction, Brunauer Emmett-Teller, thermogravimetric analysis, and photoluminescence. The hybrid sonophotocatalysis system achieved 98.73 ± 1.25% degradation of RhB under the conditions: RhB dye concentration = 10 ppm, 4 wt% of Zr doped ZnO = 0.1 g, reaction temperature = 30 °C, time = 60 min, pH = 7. A kinetic model was developed to predict the efficiency of RhB degradation through intrinsic elementary chemical reactions. The high coefficient of determination (R2 = 0.96) indicates the model's prediction accuracy in describing the degradation kinetics of RhB within sonophotocatalysis system. The electrical energy per order (EEO) analysis demonstrated that US + UVC + 4 wt% of Zr doped ZnO significantly reduced EEO (1055 kWh m−3 order−1). The synergy index for this combination was approximately 1.60, demonstrating a significant synergistic effect. Density Functional Theory (DFT) studies were utilized to propose the most probable degradation pathway, identifying reactive sites and potential byproducts. The simulations revealed the central carbon atom (1C site) as highly susceptible to radical attacks, indicating potential decolorization pathways such as N-de-ethylation, chromophore cleavage, and ring opening. Toxicity assessments of both the parent dye and its intermediates were conducted using ECOSAR (Ecological Structure Activity Relationship) to evaluate their ecological impacts. The combination of experimental results and kinetic modeling and simulations offers a deep understanding of RhB degradation complexities, driving advancements in sustainable water treatment technologies.

Stabilize the oxygen vacancies in 2D bipyramidal CoFe2O4 via altering local electronic structure by SnSe for boosted photocatalytic degradation of ciprofloxacin: Interfacial engineering, mechanism insight and toxicological evaluation of byproducts

Investigating a cost-effective, environmentally friendly, and improved photocatalysis system for ciprofloxacin (CIPRO) degradation presents a significant hurdle in environmental remediation. In this work, SnSe nanoparticles (NPs) were synthesized by hydrothermal approach leading to the successful formation of SnSe-CoFe2O4 nanocomposite (SCF NCs). It was achieved by decorating the surface of SnSe NPs with 2D bipyramidal oxygen-vacant (OV) CoFe2O4 NPs. This work aims to stabilize the OV in 2D bipyramidal CoFe2O4 by altering the local electronic structure through SnSe, enhancing the photocatalytic degradation of CIPRO. The NPs surface morphological features, high crystalline nature, and enhanced surface area properties are investigated using several characterization techniques. The X-ray photoelectron spectroscopy (XPS) reveals the oxygen defect site in CoFe2O4 and the interfacial electric field between SnSe and CoFe2O4 NPs, significantly improving the catalytic activity of SCF NCs. The degradation of CIPRO at the optimized concentration (50 mg/L – SCF NCs, 10 mg/L CIPRO, pH - 3) under visible light reached around 91.3%. The SCF NCs demonstrate superior photodegradation performance of 2.59 and 1.86 times greater activity compared to their individual counter parts, SnSe and CoFe2O4, respectively. Furthermore, the system accommodates a broad range of degradation concentrations of CIPRO from 5 – 25 mg/L, indicating promising potential for practical applications. Additionally, the intermediate compounds formed during the photodegradation process were analyzed using gas chromatography-mass spectrometry (GC-MS), and a possible degradation pathway was proposed. The toxicity levels of these intermediates were assessed in various aquatic organisms, including fish, daphnia, and green algae using the ecological structure activity relationship (ECOSAR) tools. This research presents a new perspective on the development of innovative materials for the removal of pollutants from water sources.

Sequential DBD plasma-assisted tandem tri-electrodes Fenton process for enhanced antibiotics treatment and denitrification

Ozone generated by dielectric barrier discharge (DBD) plasma has the potential for water treatment; however, its limitations, including water solubility, performance in complex matrices, and resistance to some pollutants. This study explored a sequential DBD plasma assisted by a tandem tri-electrode Fenton (S-PEF) process, using a three-stage treatment approach for degrading antibiotics (sulfamethoxazole, SMX; amoxicillin, AMX; and norfloxacin, NOF) in continuous flow mode for 220-bed volumes. Initially, antibiotics such as SMX and AMX underwent degradation in DBD plasma gas, which housed the mixing chamber. The more resilient NOF was removed by hydroxyl radicals (OH) in the following anodic chamber of the tandem trielectrodes by Fenton assisted oxidation. The continuous cyclic redox regeneration of Fe in tandem trielectrodes prevents secondary Fe sludge pollution. Finally, NO3-N and NO2-N were denitrified into N2 with 95 % selectivity in a cathodic chamber using copper oxide nanowires. This sequential treatment is crucial to mitigating the competitive effects of CO32− and humic acid in wastewater since O3 is less susceptible to them compared to OH. The S-PEF completely degraded all antibiotics regardless of water temperature (10 and 25 °C) compared to sole plasma treatment. Finally, toxicity assessments using an ecological structure–activity relationship (ECOSAR) and E. coli disinfection assays showed a significant reduction in toxicity. This study highlights the promising potential of the S-PEF as an advanced technology for wastewater treatment.

Comprehensive analysis of biotransformation pathways and products of chloramphenicol by Raoultella Ornithinolytica CT3: Pathway elucidation and toxicity assessment

Microbial degradation of chloramphenicol (CAP) has become important for reducing the adverse impact of environmental pollution with antibiotics. Although several pathways for CAP degradation have been identified in various bacteria, multiple metabolic pathways and their respective intermediate metabolites within a single strain are rarely reported. Here, Raoultella ornithinolytica CT3 was first isolated from silkworm excrement using CAP as the sole carbon source, and 100 mg/L CAP was almost completely degraded within 48 h. The biodegradation type of CAP followed first-order kinetics. Twenty-two CAP biotransformation products were identified using high-performance liquid chromatography and ultra-high-performance liquid chromatography coupled with high-resolution mass spectrometry. The CAP biotransformation pathways were predicted mainly in the acetylation and auxiliary pathways of propionylation and butyrylation. The toxicity of CAP biotransformation products was evaluated using the ecological structure-activity relationship (ECOSAR) model and biological indicators. The results showed that the toxicity of the intermediate metabolites changed slightly, but the final metabolite was harmless to the environment. Genomic analysis predicted that genes encoding acetyltransferase, amido-linkage hydrolase, nitroreductase, haloacetate dehalogenase, and protocatechuate 3,4-dioxygenase were associated with CAP biodegradation. This study provides new insights into the microbial degradation pathway of CAP and constitutes an ecological safety assessment for CAP-contaminated environments.

Efficiency and mechanistic insights of photocatalytic degradation and sterilization utilizing g-C3N4/WO3-x Z-scheme heterojunction under full-spectrum light

Designing highly efficient full-spectrum responsive Z-scheme heterojunction for wastewater decontamination and disinfection is urgently essential. Herein, a novel Z-scheme g-C3N4/WO3-x heterojunction was successfully synthesized by a facile wet impregnation method for the highly efficient photocatalytic degradation and sterilization. Benefiting from the accelerated charge separation, broadened light absorption to near infrared region, and appropriate band energy, optimized g-C3N4/WO3-x heterojunction exhibited photocatalytic degradation of 86.3 % and 97.4 % tetracycline in 2 h under visible light and full-spectrum light, respectively. Meanwhile, 6.5-log of Escherichia coli strains could also be inactivated by optimized g-C3N4/WO3-x heterojunction within 45 min and 15 min under visible light and full-spectrum light, respectively. Impressively, it also exhibited desirable anti-interference ability and satisfying photocatalytic degradation capacity with various key experimental parameters. The plausible degradation pathways of TC and the main active species involved in the photocatalysis were investigated based on liquid chromatography-mass spectrometer (LC-MS) and electron paramagnetic resonance (EPR) analysis. Mineralization process of TC was further confirmed by three-dimensional fluorescence spectra (3D EMMs). Besides, Toxicity Estimation Software Tool (T.E.S.T.) and Ecological Structure-Activity Relationships (ECOSAR) program were applied to predict the noxiousness of TC and its potential intermediates. The results suggested that the excitotoxicity of intermediates generally decreased relative to the pristine TC. Finally, we propose a plausible enhancement mechanism of photocatalytic degradation and sterilization. This work sheds a new light on the design of novel full-spectrum responsive Z-scheme heterojunction for environmental remediation.

Weak magnetic field for enhanced degradation of sulfamethoxazole by the CoFe2O4/PAA system: Insights into performance and mechanism

In this work, a novel approach coupling a heterogeneous weak magnetic field (WMF) with the CoFe2O4/peroxyacetic acid (PAA) system was employed to enhance the degradation of sulfamethoxazole (SMX). Under the optimized conditions of 50 mT WMF, 0.1 g/L CoFe2O4, 0.2 mM PAA, and initial pH 6.0, a complete degradation of 10 μM SMX was achieved in 25 min, exhibiting a high synergistic coefficient of 1.61. This result indicates a significant synergistic effect among WMF, CoFe2O4, and PAA in effectively degrading SMX. The introduction of WMF did not alter the pH application range of the CoFe2O4/PAA system. Furthermore, the degradation efficiency of SMX by the CoFe2O4/PAA/WMF system was significantly reduced in the presence of humic acid (HA) and bicarbonate ions (HCO3−), while chloride ions (Cl−) exhibited a minor inhibitory effect. Quenching experiments and electron paramagnetic resonance (EPR) analysis reveal that WMF did not alter the types of reactive oxygen species (ROS) generated in the CoFe2O4/PAA system. The degradation of SMX in the CoFe2O4/PAA/WMF system involved both radical (CH3C(O)O∙ and CH3C(O)OO∙) and non-radical (1O2) oxidation pathways, driven by the redox cycling between ≡Co2+/≡Co3+ and PAA, as well as the rapid adsorption and transformation of oxygen (O2) at oxygen vacancies (OV), respectively. The presence of WMF enhanced the utilization of PAA by CoFe2O4 by improving the convection and mass transport in the solution, facilitating the formation of superoxide anion (O2∙−) and supplemented lattice oxygen (O2−) through the directional migration of paramagnetic O2 towards the CoFe2O4 surface, thus significantly promoting ROS formation. Additionally, the degradation pathways of SMX in the CoFe2O4/PAA/WMF system were proposed based on density functional theory (DFT) calculations and the detected transformation products (TPs). The toxicity of SMX was effectively reduced, as verified by predictions from the Ecological Structure-Activity Relationship Model (ECOSAR) procedure. The excellent catalytic performance, reusability, and effective degradation of various organic pollutants demonstrated by the CoFe2O4/PAA/WMF system suggest its potential as a promising strategy for water treatment.

Enhanced simazine degradation via peroxymonosulfate activation using hemin-doped rice husk biochar as a novel Fe/N–C catalyst

The presence of herbicides, including simazine (SIM), in aquatic environments pose significant threats to these ecosystems, necessitating a method for their removal. In this study, a hemin-doped rice husk-derived biochar (RBC@Hemin20%) was synthesized using a simple, one-step pyrolysis, and its degradation efficiency towards SIM via peroxymonosulfate (PMS) was assessed. Under optimized conditions (hemin loading = 20 wt%, SIM = 0.5 ppm, RBC@Hemin20% catalyst = 0.2 g L−1, PMS = 2.0 mM, and pH = 5.84 [unadjusted]), RBC@Hemin20%, as an Fe/N–C catalyst, could activate PMS to achieve >99% degradation of SIM. Based on radical scavenger and electron spin resonance spectroscopy (ESR) experiments, both radical (•OH and SO4•−) and non-radical (such as singlet oxygen, 1O2) mechanisms and electron transfer were involved in the degradation system. Significant mineralization (97.3%) and reusability efficiency (∼74.1% SIM degradation after 4 applications) were exhibited by the RBC@Hemin20%/PMS system, which also maintained a remarkable degradation efficiency in tap-, river-, and ground-water. Additionally, the RBC@Hemin20%/PMS system exhibited rapid degradation of tetracycline (TC) and diclofenac (DCF), indicating its prospects in the degradation of other organic pollutants of aquatic environments. The plausible degradation mechanism pathways of SIM are proposed based on identified intermediates. Finally, the toxicity of these intermediate products is analysed using the Ecological Structure Activity Relationship (ECOSAR) software. It is expected that this study will expand the current knowledge on the synthesis of efficient biomass-based Fe/N–C composites for the removal of organic pollutants in water.

Integration of vacuum UV/peroxydisulfate and reductive processes for the thorough defluorination of 8:3 fluorotelomer carboxylates: The critical contribution of preoxidation

Fluorotelomers have been systematically developed in bulk quantities and extensively applied in the fluoropolymer industry. Reductive treatments of fluorotelomers are different from those of perfluoroalkyl substances. In this study, vacuum UV/peroxydisulfate (VUV/PDS) was used for the first time to preoxidize 8:3 fluorotelomer carboxylates (8:3FTCA). Subsequently, it was integrated with the VUV/sulfite/iodide reductive process to accomplish the comprehensive defluorination of the oxidized products. The performance and mechanisms of 8:3FTCA degradation in the preoxidation process were mainly explored. pH values from 6.0 to 8.0 were conducive to 8:3FTCA decomposition. Hydrogen peroxide, hydroxyl radical (•OH), and hydroperoxyl radical (HO2•) were observed to be in a dynamic equilibrium state of mutual transformation, and the contributions of •OH and HO2• were 76.8 % and 17.4 %, respectively. The investigation of the influences of background water matrices demonstrated minimal adverse effects of sulfate and chloride, whereas bicarbonate, carbonate, and natural organic matter exhibited inhibitory effects. The degradation pathways of 8:3FTCA were speculated through density functional theory calculation and intermediate identification. The Ecological Structure–Activity Relationships simulation showed that VUV/PDS preoxidation decreased the aquatic toxicity of 8:3FTCA. These findings provide valuable insights for addressing challenges associated with fluorotelomer carboxylates.

Quantitative and mechanistic elucidation of the reactive oxygen species for effective sulfamethoxazole removal in heterogeneous peroxymonosulfate activated by MOFs-derived cladding structure CoZn/NC@UiO

In cobalt-based catalyst/peroxymonosulfate (PMS) systems, the key issues are the leaching of metals and the stability of catalysts. In this study, a NH2-UiO-66 cladded CoZn/NC catalyst was synthesized for efficient degradation of sulfamethoxazole (SMX) using activated PMS. The removal efficiency of SMX could achieve 100% within 30 min. The leaching of Co2+ was inhibited to 0.05 ppm and the anti-interference and cyclic stability of the catalyst were enhanced by the NH2-UiO-66 shell. In addition, the quenching experiment, electron paramagnetic resonance (EPR) technique and probe experiment were used to analyze the reactive oxygen species (ROSs) qualitatively and quantitatively. The findings demonstrated that singlet oxygen (1O2) had the highest steady-state and cumulative concentration. However, 1O2 could only participate in the degradation of SMX through single electron transfer or addition reaction, resulting in a lower second-order rate constant of the SMX reaction with 1O2. Sulfate radical (SO4·-) contributed the most to the degradation of SMX due to the high reactivity of the sulfonamide structure in SMX to SO4·-. Finally, possible pathways for SMX degradation were proposed. The two primary mechanisms of SMX degradation were S-N cleavage and amino hydroxylation/oxidation. The toxicity of most of the intermediates was less than that of SMX through ecological structure–activity relationship analysis. Overall, a novel approach to synthesize low leaching and efficient cobalt based catalyst was put forward, and the activation mechanism of PMS was also revealed.

Deciphering the degradation of sulfonamides by UV/chlorination in aqueous solution: kinetics, reaction pathways, and toxicological evolution

UV/Cl is a cost-effective process and is often used in municipal water treatment plants as well as in industrial applications. UV/Cl method is found highly effective in degrading contaminants, including pathogens, The conventional methods for water treatment have been proven inefficient for the complete elimination of pollutants and generate harmful by-products in the environment. This study evaluated the efficacy of three different treatment methods, chlorination alone, UV photolysis, and UV/Cl, for the degradation of sulfonamides (SAs) in water. The results highlighted that UV/Cl treatment was an efficient method for enhancing the degradation of sulfisoxazole (SFX), sulfadimethoxine (SAT), and sulfaguanidine (SG), with substrates degrading in 5, 6.5, and 4 min. The study also investigated the reactive species generated in the UV/Cl system and found that ·OH was the species responsible for the elimination of SFX. Additionally, the study explored the intermediate products generated during the degradation of SFX under the UV/Cl system, identifying VI distinct degradation pathways. The presence of ·OH radicals significantly enhanced the degradation of SFX, while some chlorine species also contributed to the degradation. The study predicted the toxicity of degradation products from the UV/Cl system using the ECOSAR (Ecological Structure Activity Relationships) program and found that the final degradation products of SFX were non-toxic, but concerns were raised about acute toxicity.

A novel visible light-driven oxygen doped C3N4/Bi12O17Cl2/ferrate(VI) system for Bisphenol A degradation: Radical and nonradical pathways

In this study, visible light-activated photocatalyst oxygen-doped C3N4@Bi12O17Cl2 (OCN@BOC) and Fe(VI) coupling system was proposed for the efficient degradation of bisphenol A (BPA). The comprehensive characterization of the OCN@BOC photocatalyst revealed its excellent photogenerated carrier separation rate in heterogeneous structures. The OCN@BOC/Fe(VI)/Vis system exhibited a remarkable BPA removal efficiency of over 84% within 5 min. Comparatively, only 37% and 59% of BPA were degraded by single OCN@BOC and Fe(VI) in 5 min, respectively. Reactive species scavenging experiments, phenyl sulfoxide transformation experiments, and electron paramagnetic resonance experiments confirmed the involvement of superoxide radicals (⋅O2−), singlet oxygen (1O2), as well as iron(V)/iron(IV) (Fe(V)/Fe(IV)) species in the degradation process of BPA. Furthermore, density functional theoretical calculations and identification of intermediates provided insights into the potential degradation mechanism of BPA during these reactions. Additionally, simulation evaluations using an ecological structure activity relationship model demonstrated that the toxicity of BPA to the ecological environment was mitigated during its degradation process. This study presented a novel strategy for removing BPA utilizing visible light photocatalysts, highlighting promising applications for practical water environment remediation with the OCN@BOC/Fe(VI)/Vis system.

Assessing ecotoxicity, removal efficiency, and molecular response of freshwater microalgae to bisphenol AP

Bisphenol AP (BPAP), an analog of BPA and endocrine disrupter, is increasingly being detected in water, signaling its rise as an environmental contaminant similar to BPA, which is known for its health implications. This study investigated the ecotoxicity of BPAP in four freshwater microalgae (Chlorella sorokiniana, Chlamydomonas mexicana, Scenedesmus obliquus, and Chlorella vulgaris), along with their removal potential and biotransformation. This was followed by de novo transcriptomic analysis to elucidate the molecular response after BPAP exposure. The toxicity (120 h-EC50) of BPAP for microalgal species ranged from 1.509 mg L−1 to 6.509 mg L−1. C. mexicana exhibited the highest removal efficiency of 86.5 % after 12 days, followed by C. vulgaris (86.0 %), S. obliquus (78.9 %), and C. Sorokiniana (56.5 %) at 1 mg L−1. Eight biotransformed BPAP products were analyzed, and their toxicity was predicted to be lower than that of BPAP using the Ecological Structure Activity Relationships software. Transcriptomic analysis of C. mexicana revealed the differential expression of 4611 genes in processes related to metabolism, cellular activities, and stress responses. Genes encoding methyltransferases, glycosyltransferases, and various oxidoreductases, including electron-transferring flavoprotein dehydrogenase and glutaredoxin, were significantly upregulated in algal cells exposed to BPAP, suggesting the potential of C. mexicana for BPAP detoxification via glycosylation and transmethylation. These results offer novel insights into the ecotoxicity, removal potential, and biotransformation of BPAP in freshwater microalgae, with transcriptomic analysis, elucidating the molecular mechanisms of BPAP detoxification for effective environmental remediation.

Degradation of Isotianil in Water and Soil: Kinetics, Degradation Pathways, Mechanisms, and Ecotoxicity Assessments.

Pesticides are transported and transformed in soil and can enter surface water through various pathways. They undergo hydrolysis, oxidation, and photoconversion in surface water. Isotianil is a new fungicide that effectively controls rice blast. However, there are limited reports on its degradation. Herein, the hydrolysis and photolysis of isotianil in water and its degradation in soil samples from five provinces of China were investigated. The degradation products of isotianil were identified using ultrahigh-performance liquid chromatography-Q exactive hybrid quadrupole-orbitrap high-resolution accurate mass spectrometry, and four compounds were discovered for the first time. The degradation pathways of isotianil were inferred, and the reaction active site and degradation mechanism of isotianil were clarified based on density functional theory calculations. The ecotoxicity of the degradation product M118 (aminobenzonitrile) was found to be moderate toward Daphnia magna, which was predicted and confirmed by Ecological Structure Activity Relationships and the experiment, respectively. The results of this study will contribute to a better understanding of the fate of isotianil in the environment.

Percarbonate mediated advanced oxidation of irbesartan: A suitable alternative to chlorination?

This study aims to investigate the environmental fate of irbesartan when subjected to activated percarbonate treatment. The investigation delves into the formation of disinfection byproducts (DBPs) and evaluates their toxicity, and it seeks to draw comparisons with outcomes from treatment with sodium hypochlorite, already characterized in previous findings. The proposed treatment indicates the formation of at least 11 DBPs - eight identified for the first time - which have been isolated by various chromatographic techniques, identified by Nuclear Magnetic Resonance and Mass Spectrometry studies and for which a mechanism has been proposed to elucidate their formation. To evaluate irbesartan's biological impact during treatment with sodium percarbonate (SPC), a toxicity study of the DBPs was conducted using Daphnia magna, Aliivibrio fischeri, and Raphidocelis subcapitata, three model organisms. The ecotoxicity was evaluated using the Ecological Structure-Activity Relationships (ECOSAR) computer program and compared with experimental results. Compared to chlorination treatment, a lower mineralization percentage (−43 %) and amount of DBPs at least twice higher were observed. Toxicity assessment highlighted that DBPs formed during SPC treatment were more toxic than those from chlorination. ECOSAR predicted toxicity aligned with experimental findings. Additionally, the DBPs exhibited varying levels of toxicity, primarily attributable to the presence of aromatic and hydroxyl groups in their chemical structure, indicating that SPC treatment is not suitable for treatment of irbesartan polluted waters.