Ecological Structure Activity Relationships Research Articles

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.

BiVO4-Driven photocatalytic degradation of pharmaceutical in Slurry Bubble Column Reactor: Influencing factors and toxicological profiling

As the pursuit for sustainable and effective solutions to address environmental pollution intensifies, a comprehensive approach in photocatalysis has become a subject of increasing interest. In this study, BiVO4 photocatalyst synthesized through a pH-controlled hydrothermal method was used for the degradation of tetracycline (TET), a prevalent pharmaceutical pollutant. Optimal conditions, particularly a pH of 9 and enriched dissolved oxygen (DO), significantly improve TET removal, achieving a 96 % degradation efficiency with a rate constant of k = 0.1069 min−1. The investigation revealed that the degradation predominantly involves the generation of reactive oxygen species (ROS), notably O2•−, which play a crucial role in the degradation of TET. Using the “ecological structure–activity relationships” (ECOSAR) program, the toxicity of the intermediates was assessed, highlighting the environmental implications of the photocatalytic process. In addressing the scalability for industrial applications, a Slurry Bubble Column Reactor (SBCR) was employed, and separation-stability tests of the photocatalyst were conducted. These tests confirmed the photocatalyst’s long-term effectiveness and stability, underscoring its potential for repeated use in large-scale applications. This comprehensive research not only underscores the potential of BiVO4 in removing environmental contaminants but also provides vital insights into ecological safety.

BiVO4-Driven photocatalytic degradation of pharmaceutical in Slurry Bubble Column Reactor: Influencing factors and toxicological profiling

As the pursuit for sustainable and effective solutions to address environmental pollution intensifies, a comprehensive approach in photocatalysis has become a subject of increasing interest. In this study, BiVO4 photocatalyst synthesized through a pH-controlled hydrothermal method was used for the degradation of tetracycline (TET), a prevalent pharmaceutical pollutant. Optimal conditions, particularly a pH of 9 and enriched dissolved oxygen (DO), significantly improve TET removal, achieving a 96 % degradation efficiency with a rate constant of k = 0.1069 min−1. The investigation revealed that the degradation predominantly involves the generation of reactive oxygen species (ROS), notably O2•−, which play a crucial role in the degradation of TET. Using the “ecological structure–activity relationships” (ECOSAR) program, the toxicity of the intermediates was assessed, highlighting the environmental implications of the photocatalytic process. In addressing the scalability for industrial applications, a Slurry Bubble Column Reactor (SBCR) was employed, and separation-stability tests of the photocatalyst were conducted. These tests confirmed the photocatalyst’s long-term effectiveness and stability, underscoring its potential for repeated use in large-scale applications. This comprehensive research not only underscores the potential of BiVO4 in removing environmental contaminants but also provides vital insights into ecological safety.

BiVO4-Driven photocatalytic degradation of pharmaceutical in Slurry Bubble Column Reactor: Influencing factors and toxicological profiling

As the pursuit for sustainable and effective solutions to address environmental pollution intensifies, a comprehensive approach in photocatalysis has become a subject of increasing interest. In this study, BiVO4 photocatalyst synthesized through a pH-controlled hydrothermal method was used for the degradation of tetracycline (TET), a prevalent pharmaceutical pollutant. Optimal conditions, particularly a pH of 9 and enriched dissolved oxygen (DO), significantly improve TET removal, achieving a 96 % degradation efficiency with a rate constant of k = 0.1069 min−1. The investigation revealed that the degradation predominantly involves the generation of reactive oxygen species (ROS), notably O2•−, which play a crucial role in the degradation of TET. Using the “ecological structure–activity relationships” (ECOSAR) program, the toxicity of the intermediates was assessed, highlighting the environmental implications of the photocatalytic process. In addressing the scalability for industrial applications, a Slurry Bubble Column Reactor (SBCR) was employed, and separation-stability tests of the photocatalyst were conducted. These tests confirmed the photocatalyst’s long-term effectiveness and stability, underscoring its potential for repeated use in large-scale applications. This comprehensive research not only underscores the potential of BiVO4 in removing environmental contaminants but also provides vital insights into ecological safety.

Effects of ball milling on hydrochar for integrated adsorption and photocatalysis performance

In this study, hydrochar (HC) was firstly treated by ball milling for methylene blue (MB) removal through combined adsorption-photodegradation. The ball-milled bamboo hydrochar (BM-HC) exhibited a maximum adsorption capacity of 49.522 mg/g and a synergistic adsorption-photodegradation removal rate of 95.22% within 30 min, which was superior to those of pristine HC (20.530 mg/g, 79.47%). Compared with HC, BM-HC had smaller particle size, increased quantities of polyfuran rings, enhanced adsorption of visible light, which were favorable for the enhancement of adsorption capacity and photodegradation rate. The effect of the catalyst dosage, MB concentration, water matrix, pH, coexisting ions on MB photodegradation were examined. The possible synergistic adsorption and photodegradation mechanism of MB was illustrated. The foremost active specie in the synergistic removal of MB was h+. In addition, the possible degradation pathways of MB were proposed depending on the intermediates detected by Liquid chromatography-mass spectrometry (LC-MS), and the biotoxicity of MB and its intermediates was evaluated by Ecological Structure-Activity Relationship (ECOSAR) program. This work confirms that ball-milled hydrochar could be used as a potential catalyst for pollutants removal in water via synergistic adsorption and photocatalysis.

Elucidating the photodegradation mechanism of octylisothiazolinone and dichlorooctylisothiazolinone in surface water: An in-depth comprehensive analysis

Octylisothiazolinone (OIT) and Dichlorooctylisothiazolinone (DCOIT), widely used antibacterial agents in coatings, have seen a sharp increase in use in response to the Coronavirus disease 2019 (Covid-19) pandemic, ultimately leading to their increase in the aquatic environment. However, their photodegradation process in surface water is still unclear. The purpose of this study is to investigate the photodegradation kinetics and mechanisms of OIT and DCOIT in natural water environments. Under simulated solar irradiation, they undergo direct photolysis in both natural freshwater and seawater mainly via their excited singlet states, while no self-sensitization photolysis was observed. The direct photolysis rate constants of OIT and DCOIT were 1.19 ± 0.07 and 0.57 ± 0.03 h−1, respectively. In addition, dissolved organic matter (DOM), NO3− and Cl− in natural waters did not contribute significantly to the photodegradation, and the light screening effect of DOM was identified as the main inhibiting factor. The photodegradation half-life of OIT was estimated to be 0.66 to 1.69 days, while the half-life of DCOIT was as high as 20.9 days during winter in surface water at 30°N latitude. Ring opening of the N-S bond and covalent bond breaking between CN are the main pathways for the photodegradation of OIT and DCOIT, which is verified by density-functional theory calculations. Ecological Structure Activity Relationships (ECOSAR) results indicate that OIT and DCOIT have “Very Toxic” biological toxicity, and the acute toxicity of their products is significantly reduced. It is noteworthy that the toxicity of the products of DCOIT is generally higher than that of OIT, and the chronic toxicity of most of the products is still above the “Toxic” level. Therefore, an in-depth understanding of the photodegradation mechanisms of OIT and DCOIT in aqueous environments is crucial for accurately assessing their ecological risks in natural water environments.

Novel indazolylchromones: synthesis, fungicidal evaluation, molecular docking and aquatic toxicity prediction.

Fungal diseases cause substantial loss to agricultural crops, affecting both quantities and quality. Although several methods are used for preventing disease incidence, fungicides remain crucial for higher yields and better quality. But in the past, the efficacy of several fungicides has decreased due to increased cases of fungicide resistant. In our pursuit of new effective fungicides, we synthesised a series of twenty 2-Indazol-1-yl-chromen-4-one derivatives (6a- 6t). The characterization of synthesized compounds was performed by several spectroscopic methods including Infrared, Nuclear Magnetic Resonance (1H and 13C) and HRMS. Out of 20 synthesised compounds, 19 (6b- 6t) were found to be novel. All synthesised indazolylchromones showed very good antifungal activity against Sclerotium rolfsii and Fusarium oxysporum. Among the tested compounds, 6t and 6f exhibited very good fungicidal activity against S. rolfsii with an ED50 of 10.10mgL-1 and 16.18mgL-1, respectively. In case of Fusarium oxysporum compound 6f displayed good' activity with an ED50 value of 27.82mgL-1. Molecular docking study was done to predict the binding sites of most active compounds, 6t and 6f with Cytochrome P450 14alpha -sterol demethylase (CYP51) enzyme using molsoft software. The acute toxicity predictions the of synthesized compounds for fish (LC50,96 Hr), daphnid (LC50, 48 Hr) and green algae (EC50, 96Hr) and the chronic toxicity predictions (ChV) were assessed using Ecological Structure Activity Relationship (ECOSAR) model. As per ECOSAR prediction, all the chemicals are inside AD and not missing predictions.

Construction of novel S-defects rich ZnCdS nanoparticles for synergistic visible light assisted photocatalytic degradation of rhodamine B: Insights into mechanism, pathway and by-products toxicity evaluation

The contamination of wastewater by azo dyes indicates serious environmental risks. Currently, industries worldwide use approximately 700,000 tons of these dyes annually, making their removal a significant challenge. In photocatalysis research, a prominent area of dedication to the advancement of visible light photocatalysis aims to achieve superior performance in overall activity. In this study, we fabricated ZnCdS nanoparticles (NPs) via a simple co-precipitation strategy, and sulphur (S)-defect-rich ZnCdS NPs (D-ZnCdS) were created through the ball milling method. These S-defect nanoparticle (NPs) catalysts were utilized for rhodamine B (RhB) dye photocatalytic degradation experiment. (XRD) X-ray diffractometer, X-ray photoelectron spectroscopy (XPS), surface-enhanced Raman spectroscopy, and photoluminescence (PL) spectroscopy characterization studies explained the induced S-defect rich in D-ZnCdS NPs. Further, the morphological, band gap determination, and photogenerated charge carrier recombination efficiency were studied using different analytical and spectroscopic characterization techniques. The Brunauer-emmett-teller (BET) results indicate the increased surface area of D-ZnCdS NPs thereby providing more active sites. The photocatalytic degrading efficiency of D-ZnCdS over RhB explains the complete degradation of pollutants within 260 min. This enhancement in the catalytic process is attributed to the increased absorption of photon energy from the visible light and large defect-rich active sites. Further, the involvement of hydroxyl (*OH) and superoxide radicals (O2*-) in the degradation of RhB along with the presence of sulphur defects, significantly improves the charge transfer in ZnCdS NPs. The involvement of certain factors like pH, ions, NCs catalyst and different RhB concentrations on RhB degradation was investigated. Additionally, D-ZnCdS NPs showed stable degrading capability even after six consecutive cycles of catalytic RhB degradation. The by products formed during the RhB photodegradation experiment were identified using Gas chromatography-mass spectrometer (GC-MS) analysis, and toxicity in fish, daphnia, and algae was examined using the Ecological structure-activity relationships (ECOSAR) program. From the above findings, the current research work provides a new strategy for utilizing defect-engineered D-ZnCdS NPs as a promising catalyst for various environmental remediation applications and paves a ways for manufacturing innovation.

Robust advantage of MXene/g-C3N4 loaded on Fe2WO6/BiIO4 nano-platform for chemo-peroxidase colorimetric detection of uranyl ions, antifungal properties, photocatalytic degradation of p-chlorophenol, and eco-toxicity studies

In this study, we have designed a nanocomposites based on MXene/g-C3N4 (MX/CN) loaded on Fe2WO6/BiIO4 (FWO/BIO) for different applications. The nanocomposites were identified by using the structural and morphological studies including XRD, FESEM, EDS, DLS, TGA, BET, UV–vis, XPS techniques. The average sizes of BIO, FWO/BIO, and MX/CN/FWO/BIO were 44, 46, and 58 nm, respectively. The synthesized MX/CN/FWO/BIO nanocomposites was utilized for the peroxidase colorimetric identification of uranyl ions (UO22+) with the excellent selectivity and sensitivity properties (LOD: 3.21 nM). The antifungal efficiency of the as-fabricated nanomaterials was investigated and the inhibition zone at high concentration 2.5 mg/mL of MX/CN/FWO/BIO nanocomposites were 19.74, 17.91, 24.25, and 21.32 mm against Aspergillus spp., Penicillum spp., Candida spp. and Fusarium spp., respectively. The MX/CN/FWO/BIO nanocomposites was utilized in photocatalysis process for decomposition of p-chlorophenol under visible light lamp. The findings showed that the MX/CN/FWO/BIO nanocomposites can be degrade p-chlorophenol (100.0 %) under visible light irradiation (80 min). The photocatalytic response was decreased about 2 % after 5th cycle times, and showed the best stability of the MX/CN/FWO/BIO nanocomposites. The quenching test shows the mechanism of p-chlorophenol degradation was conducted by •O2−, and •OH species. Additionally, the ecological structure activity relationships ECOSAR software was utilized to evaluate the toxicity of the p-chlorophenol and the intermediates produced. This work can lead for manufacturing innovation in near future.

Periodate activation by MnFe2O4 spinel for sulfamethoxazole degradation: Iodate radical dominance, degradation pathway, DFT calculation and toxicity assessment

This study synthesized spinel MnFe2O4 at different temperatures, which was applied to activate periodate (PI) for sulfamethoxazole (SMX) degradation. It was found that the 500-MFO (MnFe2O4 calcined at 500 ℃) demonstrated superior activity in PI activation, with notable sustainability but strong substrate selectivity. Furthermore, a comprehensive analysis, including quenching experiment, electron paramagnetic resonance (EPR) technique, X-ray photoelectron spectroscopy (XPS) analysis, metal ions leaching detection, homogeneous PI activation, and methyl phenyl sulfoxide (PMSO) probe test, revealed that homo- and heterogeneous pathways as well as free and non-free radical routes coexisted in the 500-MFO/PI system. Multiple active species, including iodate radical (IO3•), hydroxyl radical (•OH), superoxide radical (O2•-), singlet oxygen (1O2), and Mn(IV) were identified, with IO3• from heterogeneous activation being the primary species. When PMSO and SMX coexisted, PMSO could react with Mn(IV), promoting the regeneration of Mn reaction sites and the production of IO3•, thereby being beneficial for the degradation of SMX. The degradation pathways of SMX were elucidated through high-performance liquid chromatography-mass spectrometry (HPLC-MS) and density functional theory (DFT) calculation. The acute and chronic toxicity of thirteen by-products to aquatic organisms were predicted using the Ecological Structure Activity Relationships (ECOSAR) software, with the corresponding results revealing that although the toxicity of intermediates fluctuated, the final products were environmentally benign. Therefore, this investigation provides a viable method for SMX degradation in wastewater treatment.

Enhanced peroxymonosulfate activation for degradation of iodinated contrast media by microwave-induced bimetallic carbon-based catalysts: Insight into the synergistic mechanism between microwaves and bimetallic sites

Microwave-assisted catalytic oxidation process was a promising wastewater treatment technology for the disposal of refractory organic contaminants. Nevertheless, its practical implementation was limited by the high energy consumption of microwaves and the poor sustainable reactivity of catalysts. To address these issues, the microwave-assisted dielectric-activation double-responsive Co/Fe carbon-based catalyst (CoFe/NC-3) was used to activate peroxymonosulfate (PMS) for oxidative degradation of refractory diatrizoate (DTZ). The results showed that the DTZ was completely degraded within 6 min in the MW/CoFe/NC-3/PMS reaction system, and the degradation efficiency increased by 82.38% compared with the MW/Fe/NC/PMS system. It was attributed to the enriched active sites and prolonged redox cycling capability of the bimetallic catalysts. Moreover, microwave enhanced electron migration ability to accelerate the circulation of Fe3+/Fe2+/Fe0 and Co3+/Co2+ and generate more reactive oxygen species (ROSs) for the high-efficiency degradation of DTZ. The degradation pathways of DTZ were elucidated by LC-MS in combination with DFT calculation and the product toxicity was evaluated using ecological structure-activity relationship software (ECOSAR). The results showed that the majority of intermediate degradation products were not acute or chronic toxicity to fish, daphnia, and green algae. Overall, these results revealed that the MW/CoFe/NC-3/PMS system was a cost-effective and stable method for wastewater treatment.

Myricetin Inhibits Photodegradation of Profenofos in Water: Pathways and Mechanisms

Profenofos is a detectable insecticide in the environment with strong toxicity to non-targeted organisms. Photodegradation is a main transformation of profenofos in the environment. Myricetin is a flavonoid that strongly scavenges free radicals. The effect of myricetin on the photodegradation of profenofos was studied. The half-lives (T1/2) of profenofos were 1.7–7.0 and 90 h under artificial light and sunlight. The photolysis rate of profenofos decreased by 1.87–4.72 and 7.62 times with the addition of 20 ratios of myricetin. Free radicals reacting with profenofos were •OH and 1O2, and the key free radical was •OH. Myricetin strongly scavenged •OH and 1O2 which rapidly reacted with profenofos. O-(2-Chlorophenyl)-O-ethyl-S-propyl phosphorothioate (M3) and O-(2-chlorophenyl)-O-ethyl phosphorothioate (M4) were major and new photoproducts of profenofos. According to the Ecological Structure Activity Relationships, photodegradation of profenofos was a detoxification process, but myricetin inhibited the photodegradation of profenofos and its photoproducts. These results highlight the implication of myricetin on the fate and potential risk of profenofos in the environment.

Green synthesis of Mn2O3 activated PDS to degrade estriol in medical wastewater and its degradation pathway

While green synthesized Mn2O3 has been used to activate peroxydisulfate (PDS) to degrade estrogens, effective application in real wastewater is less common due to variation in environmental matrices in wastewater. Here, green synthesized Mn2O3 was used as a Fenton-like catalyst to activate PDS for estriol (E3) degradation in wastewater. The results show that the high concentration of K+ and humic acid in wastewater could inhibit the activation process of the Mn2O3/PDS system, resulting in low removal efficiency of E3 in wastewater. However, when the concentration of PDS was increased to 15 mM, the removal efficiency of E3 in medical wastewater can reach 100 %, because the high PDS concentration increases the main reactive oxygen species singlet oxygen (1O2) in medical wastewater. XRD and SEM-EDS analysis indicate that the crystal structure of Mn2O3 is stable, with a consistent rice grain-like morphology before and after reaction. XPS results show no obvious changes in the percentages of Mn(II), Mn(III) and Mn(IV) before and after reaction, indicating that Mn2O3 has good stability when degrading E3 in medical wastewater. Based on density functional theory (DFT) calculations, liquid chromatography-mass spectrometry (LC-MS), and ecological structure–activity relationship (ECOSAR) modeling data analysis, the reactive oxygen species produced by the Mn2O3/PDS system mainly attack the benzene ring structure of E3, where the toxicity of its intermediate products declines significantly after breaking the benzene ring structure. Overall, this work provides greater understanding of the E3 degradation pathway and the toxicity of its degradation products.

Predicting environmental risks of pharmaceutical residues by wastewater surveillance: An analysis based on pharmaceutical sales and their excretion data

Pharmaceutical residues are increasingly becoming a significant source of environmental water pollution and ecological risk. This study, leveraging official national pharmaceutical sales statistics, predicts the environmental concentrations of 33 typical pharmaceuticals in the Tianjin area. The results show that 52 % of the drugs have a PEC/MEC (Predicted Environmental Concentration/Measured Environmental Concentration) ratio within the acceptable range of 0.5–2, including atenolol (1.21), carbamazepine (1.22), and sulfamethoxazole (0.91). Among the selected drugs, tetracycline, ciprofloxacin, and acetaminophen had the highest predicted concentrations. The EPI (Estimation Programs Interface) biodegradation model, a tool from the US Environmental Protection Agency, is used to predict the removal efficiency of compounds in wastewater treatment plants. The results indicate that the EPI predictions are acceptable for macrolide antibiotics and β-blockers, with removal rates of roxithromycin, spiramycin, acetaminophen, and carbamazepine being 14.1 %, 61.2 %, 75.1 %, and 44.5 %, respectively. However, the model proved to be less effective for fluoroquinolone antibiotics. The ECOSAR (Ecological Structure-Activity Relationships) model was used to supplement the assessment of the potential impacts of drugs on aquatic ecosystems, further refining the analysis of pharmaceutical environmental risks. By combining the concentration and detection frequency of pharmaceutical wastewater, this study identified 9 drugs with significant toxicological risks and marked another 24 drugs as substances of potential concern. Additionally, this study provides data support for addressing pharmaceutical residues of priority concern in subsequent research.

Trace Analysis of Five Androgens in Environmental Waters by Optimization of Enzymolysis and Solid-Phase Extraction Ultra-Performance Liquid Chromatography-Mass Spectrometry and its Risk Assessment.

Steroid hormones (SHs) have received widespread attention in recent years. However, current studies of SHs have primarily focused on estrogenic substances, with androgen-related studies being quite limited. We optimized the solid-phase extraction (SPE) pretreatment method, as well as the enzymolysis conditions of five androgens (androstenedione, boldenone, methandienone, nandrolone, and testosterone), to simultaneously determine their concentrations in the effluent from wastewater treatment plants and surface water samples. Then we evaluated the ecological risks of the five androgens in the effluent and Pearl River basin of Guangzhou (PR China) using the risk quotient method. The recovery rates of the targets were 90% to 99% in water samples when digested with β-glucosidase for 90 min before solid-phase extraction, extracted with a Poly-Sery HLB column, and washed with 15% methanol aqueous solution and 2% ammonia. The established instrument's limit of detection was between 0.02 and 0.39 μg/L, and the limit of quantification was between 0.05 and 1.29 μg/L. Androstenedione, boldenone, methandienone, nandrolone, and testosterone were detected in all samples from the 2018 and 2022 wastewater influent and the 2018 surface water, with concentrations of 3.06 × 101 ng/L to 1.33 × 103 ng/L, 1.03-8.15 × 102 ng/L, and 0.93 × 101 ng/L to 5.50 × 102 ng/L, respectively. The ecological risks of androgens in wastewater influent and surface water were medium to high and low to medium, respectively. Moreover, the biotoxicity of androgens was predicted by the Ecological Structure Activity Relationships model, with methandienone and androstenedione having the highest and lowest acute and chronic toxicities, respectively. These results suggest that the risk of environmental androgens should not be ignored and that further research should be carried out. Environ Toxicol Chem 2024;43:915-925. © 2023 SETAC.

Constructing oxygen defect-rich Bi2WO6/CeO2 S-scheme heterojunction for boosted photocatalytic antibiotic removal

Efficient photocatalytic eradication of antibiotic contaminant from water is of significance for the sustainability of the aquatic environment. Oxygen defective Bi2WO6/CeO2 S-scheme heterojunctions were obtained by two-step hydrothermal processes. The optimal Bi2WO6/CeO2 heterostructure (BC-10) delivered degradation efficiencies of 86.6 % and 87.1 % for tetracycline (TC) and ciprofloxacin (CIP), respectively. The boosted photocatalytic performance of BC-10 was attributed to the increased specific surface area, S-scheme construction and the formed oxygen-defect energy level which promoted the fast charge transfer and separation of photoinduced h+/e– pairs. In addition, experiments confirmed that BC-10 possessed a good catalytic performance for other organic pollutants. The toxic behavior of the TC-removal solution was verified via the Ecological Structure-Activity Relationship (ECOSAR) model and hemp-pea growth experiment, and the possible photocatalytic degradation mechanism of TC and CIP on BC-10 was proposed. This work offers an applicable construction concept of advanced photocatalysts with high redox capacity for wastewater remediation.

Degradation of pharmaceuticals in UV/H2O2 process: EEM-based kinetic model, transformation products and corresponding toxicity evaluation

Advanced oxidation process (AOP) by UV/H2O2 presented excellent performance on removing trace pharmaceuticals in wastewater. Monitoring the removal efficiency of pharmaceuticals rapidly can evaluate the effectiveness of UV/H2O2 process. And evaluating the potential risks of this technology is essential to facilitate its engineering application. In this study, diclofenac, ibuprofen, naproxen, carbamazepine and citalopram, which have potential biological effect to ecological environment, were degraded by UV/H2O2 in wastewater. Results suggested that UV/H2O2 could degrade 5 pharmaceuticals effectively. An EEM-based degradation kinetic model was constructed by combining pseudo first-order kinetic patterns of pharmaceuticals degradation and multiple exponential decay pattern of fluorescence degradation. This model could estimate the removal of pharmaceuticals rapidly and exhibited excellent predictive capability (R2 values > 0.90). Based on suspect and untargeted screening, 40 transformation products (TPs) were identified, with hydroxylation, (de)methylation and decarboxylation being the dominant pathways. Among them, 20 TPs were newly discovered. Furthermore, the predicted toxicity results from Ecological Structure-Activity Relationship (ECOSAR) model suggested that 37.5%− 42.5% of TPs exhibited higher toxicity than parent compounds. The increased toxicity of TPs of DCF and IBP could be attributed to decarboxylation. This study provides a promising and rapid method for monitoring the degradation of pharmaceuticals and estimating the toxicity of TPs. These findings facilitate further evaluation of the practicality and risks associated with the UV/H2O2 process for pharmaceutical removal in wastewater.

Accelerated removal of sulfadiazine by heterogeneous electro-Fenton system with Pt-FeOX/graphene single-atom alloy cathodes

Heterogeneous electro-Fenton (EF) process is emerging as an attractive treatment technology for removal of sulfadiazine (SDZ), in which in situ generation of H2O2 and Fe(II) are crucial steps. In this study, Pt-FeOX/G was synthesized as a heterogeneous EF catalyst by incorporating Pt single atoms into a FeOX nanocrystal. The optimized Pt1-FeOX/G cathode exhibited an SDZ conversion of >90% within 30 min over a broad pH range (3–11). The Pt1-FeOX/G cathode under a strong alkaline medium exhibited very prominent selectivity to H2O2 via 2e− oxygen reduction reaction with a maximum H2O2 concentration of 211.93 mg L−1. The hydroxyl radicals in the cathodic chamber were mainly derived from the in situ conversion of generated H2O2 in the heterogeneous EF system. The structure-activity results of Pt-FeOX/G suggested that the SDZ removal efficiency was closely related to the decentralized morphology and electronic configuration of the Pt-FeOX microcrystalline structure. Three possible SDZ degradation pathways, dominated by S–N bond cleavage, were proposed based on the stage products. The toxicity of the major products was determined using the ecological structure-activity relationship model in conjunction with trophic aquatic organisms. This study demonstrated the feasibility of enhancing heterogeneous EF catalysis for antibiotic-polluted water using multifunctional single-atom alloy cathodes.

Degradation of ciprofloxacin using magnetite nanoparticle-activated periodate: Kinetic, mechanistic and toxicity evaluation

In this study, the activation mechanisms of periodate (IO4−) by magnetite (Fe3O4) were investigated for the degradation of ciprofloxacin (CIP). Compared to standalone IO4− (PI) and Fe3O4, the combined Fe3O4/IO4− system exhibited superior degradation efficiency, especially at elevated pH levels, such as 11. Scavenger experiments revealed IO3· and IO4· as critical radicals at pH 6.5, while ·OH was the key reactive species at pH 11. X-ray photoelectron spectroscopy (XPS) identified electron transfer between Fe(II)/Fe(III) species as the main mechanism resulting in the partial reduction of Fe3O4. The study confirmed the high thermal stability of periodate and found that N2 purging reduced the degradation efficiency of the Fe3O4/PI system. High degradation efficiency was maintained in real wastewater and tap water, with Fe3O4 showing minimal structural and performance changes during repeated oxidation processes. Its magnetic properties allow for easy collection and reuse, thus minimizing costs and environmental harm. Liquid chromatography high-resolution mass spectrometry (LC-QTOF-MS) identified CIP degradation products and degradation pathways at different pH values (i.e., 3, 6.5, and 11), with piperazine ring opening and decarboxylation as the main mechanisms. Ecological Structure Activity Relationships (ECOSAR) predicted low acute and chronic toxicity to fish, daphnids and green algae for most CIP degradation products. Overall, the Fe3O4/IO4− systemoffers an efficient alternative for treating effluents containing CIPacross various water media.