Layered double hydroxide (LDH) material with abundant OH was successfully prepared by co-precipitation method, and a water purification system of Ni2Fe0.25Al0.75-LDH activated peroxymonosulfate (PMS) was constructed to rapidly degrade sulfamethoxazole (SMX) pollutants. The optimal conditions for the degradation of SMX in the system were as follows: 0.30 g/L Ni2Fe0.25Al0.75-LDH, 0.30 mM PMS, pH = 7 and 90 % SMX was removed in 10 min and almost completely in 40 min, which was consistent with the predicted results of response surface methodology (RSM) analysis. The abundant OH in Ni2Fe0.25Al0.75-LDH could form M(O)OSO3 complexes with PMS, accelerating the generation of reactive oxygen species (ROS) and promoting the removal of SMX. Quenching experiments and electron paramagnetic resonance (EPR) spectra showed that SO4-, OH, O2- and 1O2 also existed in the system. The surface-bound SO4- and O2- contributed greatly to the removal of SMX and the electron transfer between metals was also conducive to the production of active substances. The possible degradation pathways and intermediates of SMX were proposed. The toxicity assessment software tool (T.E.S.T) and total organic carbon (TOC) results indicated that the Ni2Fe0.25Al0.75-LDH/PMS system could reduce the overall environmental risk of SMX to some extent. This study provided a new strategy for the practical application of heterogeneous catalysts in sewage treatment.

The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) has been widely used around the world in both agricultural and non-agricultural fields due to its high activity. However, the heavy use of 2,4-D has resulted in serious environmental contamination, posing a significant risk to non-target organisms, including human beings. This has raised substantial concerns regarding its impact. In addition to agricultural use, accidental spills of 2,4-D can pose serious threats to human health and the ecosystem, emphasizing the importance of prompt pollution remediation. A variety of technologies have been developed to remove 2,4-D residues from the environment, such as incineration, adsorption, ozonation, photodegradation, the photo-Fenton process, and microbial degradation. Compared with traditional physical and chemical remediation methods, microorganisms are the most effective way to remediate 2,4-D pollution because of their rich species, wide distribution, and diverse metabolic pathways. Numerous studies demonstrate that the degradation of 2,4-D in the environment is primarily driven by enzymatic processes carried out by soil microorganisms. To date, a number of bacterial and fungal strains associated with 2,4-D biodegradation have been isolated, such as Sphingomonas, Pseudomonas, Cupriavidus, Achromobacter, Ochrobactrum, Mortierella, and Umbelopsis. Moreover, several key enzymes and genes responsible for 2,4-D biodegradation are also being identified. However, further in-depth research based on multi-omics is needed to elaborate their role in the evolution of novel catabolic pathways and the microbial degradation of 2,4-D. Here, this review provides a comprehensive analysis of recent progress on elucidating the degradation mechanisms of the herbicide 2,4-D, including the microbial strains responsible for its degradation, the enzymes participating in its degradation, and the associated genetic components. Furthermore, it explores the complex biochemical pathways and molecular mechanisms involved in the biodegradation of 2,4-D. In addition, molecular docking techniques are employed to identify crucial amino acids within an alpha-ketoglutarate-dependent 2,4-D dioxygenase that interacts with 2,4-D, thereby offering valuable insights that can inform the development of effective strategies for the biological remediation of this herbicide.

Photocatalysis has been proven to be an excellent technology for treating antibiotic wastewater, but the impact of each active species involved in the process on antibiotic degradation is still unclear. Therefore, the S-scheme heterojunction photocatalyst Ti3C2/g-C3N4/TiO2 was successfully synthesized using melamine and Ti3C2 as precursors by a one-step calcination method using mechanical stirring and ultrasound assistance. Its formation mechanism was studied in detail through multiple characterizations and work function calculations. The heterojunction photocatalyst not only enabled it to retain active species with strong oxidation and reduction abilities, but also significantly promoted the separation and transfer of photo-generated carriers, exhibiting an excellent degradation efficiency of 94.19 % for tetracycline (TC) within 120 min. Importantly, the priority attack sites, degradation pathways, degradation intermediates and their ecological toxicity of TC under the action of each single active species (·O2-, h+, ·OH) were first positively explored and evaluated through design experiments, Fukui function theory calculations, HPLC-MS, Escherichia coli toxicity experiments, and ECOSAR program. The results indicated that the preferred attack sites of ·O2- on TC were O20, C7, C11, O21, and N25 atoms with high f+ value. The toxicity of intermediates produced by ·O2- was also lower than those produced by h+ and ·OH.

Sulfidated nanoscale zerovalent iron (S-nZVI) has demonstrated promising reactivity and longevity for remediating chlorinated volatile compounds (cVOC) contaminants in laboratory tests. However, its effectiveness in field applications remains inadequately evaluated. This study provides the first quantitative evaluation of the long-term effectiveness of carboxymethyl cellulose-stabilized S-nZVI (CMC-S-nZVI) at a cVOC-contaminated field site. A reactive transport model-based numerical approach delineates the change in cVOC concentrations and carbon isotope values (i.e., δ13C from compound-specific stable isotope analysis (CSIA)) caused by dissolution of dense non-aqueous phase liquid, sorption, and pathway-specific degradation and production, respectively. This delineation reveals quantitative insights into remediation effectiveness typically difficult to obtain, including extent of degradation, contributions of different degradation pathways, and degradation rate coefficients. Significantly, even a year after CMC-S-nZVI application, degradation remains an important process effectively removing various cVOC contaminants (i.e., chlorinated ethenes, 1,2-dichloroethanes, and chlorinated methanes) at an extent varying from 5 %-62 %. Although the impacts of CMC-S-nZVI abundance on degradation vary for different cVOC and for different sampling locations at the site, for the primary site contaminants of tetrachloroethene and trichloroethene, their predominance of dichloroelimination pathway (≥ 88 %), high degradation rate coefficient (0.4-1.7 d-1), and occurrence at locations with relatively high CMC-S-nZVI abundance strongly indicate the effectiveness of abiotic remediation. These quantitative assessments support that CMC-S-nZVI supports sustainable ZVI-based remediation. Further, the novel numerical approach presented in this study provides a powerful tool for quantitative cVOC remediation assessments at complex field sites where multiple processes co-occur to control both concentration and CSIA data.

The bicarbonate-activated hydrogen peroxide (BAP) system is widely studied for organic pollutant degradation in wastewater treatment. Ca2Co2O5, a heterogeneous catalyst containing multivalent cobalt including Co(II) and Co(III), was herein investigated as a BAP activator, and Acid Orange 7 (AO7) was used as a model pollutant. Ca2Co2O5 exhibited good activation performance. The degradation rate and the initial rate constant of the Ca2Co2O5-activated BAP system were 5.4 and 11.2 times as high as the BAP system, respectively. The removal rate of AO7 reached 90.9% in 30 min under optimal conditions (AO7 20 mg/L, Ca2Co2O5 0.2 g/L, H2O2 1 mM, NaHCO3 5 mM, pH 8.5, 25℃). The Ca2Co2O5 catalyst exhibited good stability and recyclability, retaining 85% of AO7 removal rate in the fifth run. Compared to the BAP system, a lower dosage of H2O2 was required and a higher initial concentration of pollutants allowed for effective degradation in the Ca2Co2O5-BAP system. X-ray photoelectron spectroscopy was used to analyze the catalytic mechanism. The analysis showed that the good catalytic performance of Ca2Co2O5 attributes to its high proportion of oxygen vacancies and Co(III) species, and the presence of Ca. The active species O2•-, •OH, and 1O2 are responsible for the degradation, as indicated by the quenching experiments. The degradation mechanism of AO7 was speculated based on UV-Vis spectral analysis and the identification of degradation intermediates. The azo form, naphthalene and benzoic rings in the AO7 structure are destroyed in the decomposition. This research provides a feasible approach to designing effective and reusable BAP activators for pollutant degradation in wastewater treatment.

The ecological impact of emerging contaminants (ECs) in aquatic environments has raised concerns, particularly with regards to urine as a significant source of such contaminants in wastewater. The current investigation used the UV/Peracetic Acid (UV/PAA) processes, an innovative advanced oxidation technology, to effectively separate two emerging pollutants from urine at its source, namely, ciprofloxacin (CIP) and bisphenol A(BPA). The research findings demonstrate that the presence of the majority of characteristic ions has minimal impact on the degradation of ECs. However, in synthetic hydrolyzed urine, only NH4+ inhibits the degradation of two types of ECs, with a more pronounced effect observed on CIP degradation compared to BPA.The impact of halogen ions, specifically Cl- and I-, on the degradation of CIP in synthetic hydrolyzed urine was a complex phenomenon. When these two halogen ions are present individually, the generation of reactive halogen species (RHS) within the system enhances the degradation of CIP. However, when both types of ions coexist, the formation of diatomic radical species partially inhibits degradation. In terms of BPA degradation, while the production of reactive chlorine species (RCS) to some extent hinders the reaction rate, the generation of reactive iodine species (RIS) promotes the overall process. CIP undergoes fragmentation of the piperazine and quinoline rings, decarboxylation, defluorination reactions, as well as substitution reactions, leading to the formation of products with simplified structures. The degradation of BPA occurs gradually through hydroxyl and halogen substitution as well as isopropyl cleavage. The preliminary toxicity analysis confirmed that the presence of halogen ions in urine resulted in the formation of halogenated products in two types of ECs, albeit with an overall reduction in toxicity. The UV/PAA processes was considered to be an effective and relatively safe approach for the separation of ECs in urine.

A novel UV/oxalic acid functionalized corn straw biochar (OCBC)/peroxyacetic acid (PAA) system was built to degrade sulfadiazine from waters. 94.7 % of SDZ was removed within 30 min by UV/OCBC/PAA. The abundant surface functional groups and persistent free radicals (PFRs) on OCBC were responsible for these performances. Cyclic voltammetry (CV) and other characterization analysis revealed, under UV irradiation, the addition of OCBC served as electron donor, which might promote the reaction of electrons with PAA. The quenching and electron paramagnetic resonance (EPR) tests indicated that R-O•, 1O2 and •OH were generated. Theoretical calculations indicated sulfonamide bridge was vulnerable under the attacks of reactive species. In addition, high removal effect achieved by 5 reuse cycles and different real waters also suggested the sustainability of UV/OCBC/PAA. Overall, this study provided a feasible approach to remove SDZ with high mineralization efficiency, in addition to a potential strategy for resource utilization of corn straw.

Titanium dioxide (TiO2) based photocatalysts have been widely used as a photocatalyst for the degradation of various persistent organic compounds in water and air. The degradation mechanism involves the generation of highly reactive oxygen species, such as hydroxyl radicals, which react with organic compounds to break down their chemical bonds and ultimately mineralize them into harmless products. In the case of pharmaceutical and pesticide molecules, TiO2and modified TiO2photocatalysis effectively degrade a wide range of compounds, including antibiotics, pesticides, and herbicides. The main downside is the production of dangerous intermediate products, which are not frequently addressed in the literature that is currently available. The degradation rate of these compounds by TiO2photocatalysis depends on factors such as the chemical structure of the compounds, the concentration of the TiO2catalyst, the intensity, the light source, and the presence of other organic or inorganic species in the solution. The comprehension of the degradation mechanism is explored to gain insights into the intermediates. Additionally, the utilization of response surface methodology is addressed, offering a potential avenue for enhancing the scalability of the reactors. Overall, TiO2photocatalysis is a promising technology for the treatment of pharmaceutical and agrochemical wastewater, but further research is needed to optimize the process conditions and to understand the fate and toxicity of the degradation products.

This study investigated the degradation of aflatoxin B1 (AFB1) in food by using dual-frequency ultrasound (DFUS) and the effects of sonochemical oxidation on the efficacy. It was found that the degradation of AFB1 by bath ultrasound (BU), probe ultrasound (PU), and DFUS were all consistent with first-order kinetics. The use of DFUS significantly increased the AFB1 degradation to 91.3%, and compared with BU and PU, it increased by about 177.0% and 61.5% after 30 min treatment. DFUS could generate a synergistic effect to accelerate the generation of free radicals, which promoted sonochemical oxidation to degrade AFB1. It could be speculated that hydroxyl radical (·OH) probably acted a dominant part in the AFB1 degradation by DFUS, and the hydrogen atoms (·H) might also are contributed. These results indicated that DFUS was an effective method of AFB1 degradation.

Understanding the nitrogen isotopic variations of individual amino acids (AAs) is essential for utilizing the nitrogen isotope values of individual amino acids (δ15N-AA) as source indicators to identify proteinaceous matter originating from biomass combustion processes. However, the nitrogen isotope effects (ε) associated with the degradation of individual amino acids during combustion processes have not been previously explored. In this study, we measured the nitrogen isotope values of residual free amino acids -following a series of controlled combustion experiments at temperatures of 160-240 °C and durations of 2 min to 8 h, as described in Part 1. δ15N values of proline, aspartate, alanine, valine, glycine, leucine, and isoleucine are more positive than their initial δ15N values after prolonged combustion. Variations in δ15N values of the most AAs conform to the Rayleigh fractionation during combustion and their nitrogen isotope effects (ε) are greatly impacted by their respective combustion degradation pathways. This is the first time the ε values associated with the degradation pathways of AAs during combustion have been characterized. Only the ε values associated with Pathway 1 (dehydration to form dipeptide) and 2 (simultaneous deamination and decarboxylation) are found to be significant and temperature-dependent, ranging from + 2.9 to 6.4‰ and + 0.9‰ to + 3.8‰, respectively. Conversely, ε values associated with other pathways are minor. This improves the current understanding on the degradation mechanisms of protein nitrogen during biomass burning.