Molecular insights into effects of chemical conditioning on dissolved organic phosphorus transformation and bioavailability during sludge composting.

Phosphorus is enriched in waste activated sludge (WAS) during wastewater treatment, and organic phosphorus (OP) is a potential slow-release P fertilizer. The chemical coagulants used in sludge dewatering leave numerous residues in WAS that affect sludge composting. In this study, the effects of polyaluminum chloride (PAC) and polyferric sulfate (PFS) on the bioconversion of dissolved OP (DOP) during sludge composting were investigated. The results revealed that PFS conditioning promoted the transformation and bioavailability of DOP, whereas PAC conditioning inhibited. Results indicated that PFS conditioning enhanced the transformation of OP molecules in the thermophilic phase. Through oxidation and dehydrogenation reactions, 1-hydroxy-pentane-3,4-diol-5-phosphate and D-ribofuranose 5-phosphate with high bioactivity were generated in the PFS-conditioned compost. Enzymatic hydrolysis experiments further verified that PFS conditioning enhanced the DOP bioavailability in the compost, whereas PAC conditioning inhibited it. The study has provided molecular insights into the effects of chemical conditioning on DOP conversion during sludge composting.

Immunogenic cell death-based cancer vaccines: promising prospect in cancer therapy.

Tumor immunotherapy is a promising approach for addressing the limitations of conventional tumor treatments, such as chemotherapy and radiotherapy, which often have side effects and fail to prevent recurrence and metastasis. However, the effectiveness and sustainability of immune activation in tumor immunotherapy remain challenging. Tumor immunogenic cell death, characterized by the release of immunogenic substances, damage associated molecular patterns (DAMPs), and tumor associated antigens, from dying tumor cells (DTCs), offers a potential solution. By enhancing the immunogenicity of DTCs through the inclusion of more immunogenic antigens and stimulating factors, immunogenic cell death (ICD) based cancer vaccines can be developed as a powerful tool for immunotherapy. Integrating ICD nanoinducers into conventional treatments like chemotherapy, photodynamic therapy, photothermal therapy, sonodynamic therapy, and radiotherapy presents a novel strategy to enhance treatment efficacy and potentially improve patient outcomes. Preclinical research has identified numerous potential ICD inducers. However, effectively translating these findings into clinically relevant applications remains a critical challenge. This review aims to contribute to this endeavor by providing valuable insights into the in vitro preparation of ICD-based cancer vaccines. We explored established tools for ICD induction, followed by an exploration of personalized ICD induction strategies and vaccine designs. By sharing this knowledge, we hope to stimulate further development and advancement in the field of ICD-based cancer vaccines.

Phosphorus immobilization/release behavior of lanthanum-modified bentonite amended sediment under the dual effects of pH and dissolved organic carbon.

Lanthanum modified bentonite (LMB) is typical P-inactivating agent that has been applied in over 200 lakes. Dissolved organic carbon (DOC) and high pH restrict the phosphorus (P) immobilization performance of LMB. However, the P immobilization/release behaviors of LMB-amended sediment when suspended to overlying water with high pH and DOC have not yet been studied. In the present work, batch adsorption and long-term incubation experiments were performed to study the combined effects of pH and DOC on the P control by LMB. The results showed that the coexistence of low concentration of DOC or preloading with some DOC had a negligible effect on P binding by LMB. In the presence of DOC, the P adsorption was more pronounced at pH 7.5 and was measurably less at pH 9.5. Additionally, the pH value was the key factor that decided the P removal at low DOC concentration. The increase in pH and DOC could significantly promote the release of sediment P with a higher EPC0. Under such condition, a higher LMB dosage was needed to effectively control the P releasing from sediment. In sediment/water system with intermittent resuspension, the alkaline conditions greatly facilitated the release of sediment P and DOC, which increased from 0.087 to 0.581 mg/L, and from 11.05 to 26.56 mg/L, respectively. Under the dual effect of pH and DOC, the P-immobilization performance of LMB was weakened, and a tailor-made scheme became essential for determining the optimum dosage. The desorption experiments verified that the previously loaded phosphorus on LMB was hard to be released even under high pH and DOC conditions, with an accumulative desorption rate of less than 2%. Accordingly, to achieve the best P controlling efficiency, the application strategies depending on LMB should avoid the high DOC loading period such as the rainy season and algal blooms.

Mechanistic investigation of Pb2+ adsorption on biochar modified with sodium alginate composite zeolitic imidazolate framework-8.

For the serious situation of heavy metal pollution, the use of cheap, clean, and efficient biochar to immobilize heavy metals is a good treatment method. In this paper, SA@ZIF-8/BC was prepared for the adsorption of Pb2+ in solution using sodium alginate (SA) and zeolitic imidazolate framework-8 (ZIF-8) modified corn cob biochar. The results showed that the specific surface area of modified biochar was greatly improved, with good adsorption capacity for Pb2+, strong anti-interference ability, and good economy. At the optimal adsorption pH of 5, the adsorption model of Pb2+ by SA@ZIF-8/BC was more consistent with the pseudo-second-order kinetic model and Langmuir isotherm model. This indicates that the adsorption of Pb2+ by SA@ZIF-8/BC is chemisorption and monolayer adsorption. The maximum adsorption of modified biochar was 300 mg g-1, which was 2.38 times higher than that of before modified BC (126 mg g-1). The shift in binding energy of functional groups before and after adsorption of SA@ZIF-8/BC was studied by XPS, and it was found that hydroxyl and carboxyl groups played an important role in the adsorption of Pb2+. It was demonstrated that this novel adsorbent can be effectively used for the treatment of Pb pollution in wastewater.

Mechanistic insights into chemical conditioning on transformation of dissolved organic matter and plant biostimulants production during sludge aerobic composting.

Inorganic coagulants (aluminum and iron salt) are widely used to improve sludge dewaterability, resulting in numerous residues in dewatered sludge. Composting refers to the controlled microbial process that converts organic wastes into fertilizer, and coagulant residues in dewatered sludge can affect subsequent compost efficiency and resource recycling, which remains unclear. This work investigated the effects of two typical metal salt coagulants (poly aluminum chloride [PAC] and poly ferric sulfate [PFS]) conditioning on sludge compost. Our results revealed that PAC conditioning inhibited composting with decreased peak temperature, microbial richness, enzymatic reaction intensities, and compost quality, associated with decreased pH and microbial toxicity of aluminum. Nevertheless, PFS conditioning selectively enriched Pseudoxanthomonas sp. and resulted in more fertile compost with increased peak temperature, enzymatic reaction intensities, and humification degree. Spectroscopy and mass difference analyses indicated that PFS conditioning enhanced reaction intensities of labile biopolymers at the thermophilic stage, mainly comprising hydrolyzation (H2O), dehydrogenation (-H2, -H4), oxidation (+O1H2), and other reactions (i.e., +CH2, C2H4O1, C2H6O1). Unlike the common composting process primarily conducts humification at the cooling stage, PFS conditioning changed the main occurrence stage to the thermophilic stage. Non-targeted metabolomics revealed that indole (a humification intermediate) is responsible for the increased humification degree and indoleacetic acid content in the PFS-conditioned compost, which then promoted compost quality. Plant growth experiments further confirmed that the dissolved organic matter (DOM) in PFS-conditioned compost produced the maximum plant biomass. This study provided molecular-level evidence that PFS conditioning can promote humification and compost fertility during sludge composting, enabling chemical conditioning optimization for sustainable management of sludge.

Comparison of microbial communities in unleached and leached ionic rare earth mines.

The leaching of ionic rare earth elements has caused serious environmental pollution and ecological damage. Microorganisms play a crucial role in soil ecosystems and are one of the most important components of these systems. However, there are fewer studies related to the changes that occur in microbial community structure and diversity before and after leaching in ionic rare earth mines. In this study, Illumina high-throughput sequencing was used to examine the diversity and composition of soil microorganisms on the summit, hillside, and foot valley surfaces of unleached and leached mines after in situ leaching. The results showed that microbial diversity and abundance in the surface soil of the unleached mine were higher than those in the leached mine, and leaching had a significant impact on the microbial community of mining soil. pH was the main factor affecting the microbial community. Proteobacteria, Actinobacteriota, and Chloroflexi were phyla that showed high abundance in the soil. Network analysis showed that microbial interactions can improve microbial adaptation and stability in harsh environments. PICRUSt2 predictions indicate functional changes and linkages in soil microbial communities.

Inhibitory effect of microplastics derived organic matters on humification reaction of organics in sewage sludge under alkali-hydrothermal treatment.

Alkali-hydrothermal treatment (AHT) of sewage sludge is often used to recover value-added dissolved organic matters (DOM) enriched with artificial humic acids (HA). Microplastics (MPs), as emerging contaminants in sewage sludge, can leach organic compounds (MP-DOM) during AHT, which potentially impact the characteristics of thermally treated sludge's DOM. This study employed spectroscopy and Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR-MS) to explore the impacts of MPs on DOM composition and transformation during AHT. The biological effects of DOM were also investigated by hydroponic experiments. The results showed that the leaching of MP-DOM led to a substantial increase in DOC content of DOM of thermally treated sludge. Conversely, the HA content significantly decreased in the presence of MPs, resulting in a decline of plant growth facilitation degree. FT-ICR-MS analysis revealed that the reduction in HA content was characterized by a notable decline in the abundance of O6-7 and N1-3O6-7 molecules. Reactomics results indicated that the leaching of MP-DOM inhibited the Maillard reaction but bolstered oxidation reactions. The inhibition of Maillard reaction, resulting in a decrease in crucial precursors (dicarbonyl compounds, ketoses, and deoxyglucosone), was responsible for the decrease of HA content. The primary mechanism responsible for inhibiting the Maillard reaction was the consumption of reactive amino reactants through two pathways. Firstly, the leaching of organic acids in MP-DOM caused decrease of sludge pH, leading to the protonation of amino groups. Secondly, the lipid-like compounds in MP-DOM underwent oxidation (-2H+O), producing fatty aldehydes that consumed the reactive amino reactants. These discoveries offer enhanced insights into the specific contribution of MPs to the composition, transformation, bioactivity of DOM during AHT process.

Double-edged effect of frequent freeze-thaw on the stability of zero-valent iron after heavy metal remediation.

Freeze-thaw cycles (FTCs) cause dynamic microscale changes in ions and solvents. During freezing, heavy metals adsorbed on zero-valent iron (M-ZVI) and protons are excluded by ice crystals and concentrated in the liquid-like grain boundary region. The high proton concentration in this region leads to the dissolution of the passivation layer of ZVI. To assess the environmental risks of M-ZVI during FTCs, this study evaluated the stability of M-ZVI in this scenario from both microscale and macroscale perspectives. The results showed that the dissolution of the passivation layer had a dual effect on the stability of M-ZVI, which depends on the by-products of M-ZVI. The dissolution of the passivation layer was accompanied by the leaching of heavy metals, such as Ni-ZVI, but it also enhanced the reactivity of ZVI, causing it to re-react with desorbed heavy metals. The stability of Cr-ZVI and Cd-ZVI was improved due to frequent FTCs. Furthermore, changes in the surrounding environment (water dipole moment, ion concentration, etc.) of ZVI affected the crystallization of Fe oxides, increasing the content of amorphous Fe oxide. As low-crystallinity Fe oxides could facilitate ion doping, Ni2+ was doped into Fe3O4 lattice during FTCs, which reduced the mobility of heavy metals. Contrary to traditional views that freezing temperatures slow chemical reactions, this study provides new insights into the application of iron-based materials in cold environments.

Metagenomic analysis revealed the evolution of microbial communities, metabolic pathways, and functional genes in the heterotrophic nitrification-aerobic denitrification process under La3+ stress.

Trivalent lanthanum (La3+) exists widely in ammonia nitrogen (NH4+-N) tailing water from ionic rare earth mines; however, its effect on heterotrophic nitrification-aerobic denitrification (HN-AD) is unknown, thereby limiting the application of the HN-AD process in this field. In this study, we conducted an HN-AD process using a sequencing batch reactor (5 L) that was continuously operated to directly treat acidic (NH4)2SO4 wastewater (influent NH4+-N concentration of approximately 110 mg/L and influent pH of 5) containing different La3+ concentrations (0-100 mg/L). The NH4+-N removal efficiency of the reactor reached 98.25 % at a La3+ concentration of 100 mg/L. The reactor was in a neutral-to-alkaline environment, which favored La3+ precipitation and complexation. Metagenomic analysis revealed that the relative abundance of Thauera in the reactor remained high (88.62-92.27 %) under La3+ stress. The relative abundances of Pannonobacter and Hyphomonas significantly increased, whereas that of Azoarcus significantly decreased. Metabolic functions in the reactor were mainly contributed by Thauera, and the abundance of metabolic functions under low La3+ stress (≤5 mg/L) significantly differed from that under high La3+ stress (≥10 mg/L). The relative abundance of ammonia assimilation-related genes in the reactor was high and significantly correlated with ammonia removal. However, traditional ammonia oxidation genes were not annotated, and unknown ammonia oxidation pathways may have been present in the reactor. Moreover, La3+ stimulated amino acid biosynthesis and translocation, the citrate cycle, sulfur metabolism, and oxidative phosphorylation and promoted the overproduction of extracellular polymeric substances, which underwent complexation and adsorbed La3+ to reduce its toxicity. Our results showed that the HN-AD process had a strong tolerance to La3+, stable NH4+-N removal efficiency, the potential to recover La3+, and considerable application prospects in treating NH4+-N tailing water from ionic rare earth mines.

Nanocarrier-Mediated Immunogenic Cell Death for Melanoma Treatment.

Melanoma, a highly aggressive skin tumor, exhibits notable features including heterogeneity, a high mutational load, and innate immune escape. Despite advancements in melanoma treatment, current immunotherapies fail to fully exploit the immune system's maximum potential. Activating immunogenic cell death (ICD) holds promise in enhancing tumor cell immunogenicity, stimulating immune amplification response, improving drug sensitivity, and eliminating tumors. Nanotechnology-enabled ICD has emerged as a compelling therapeutic strategy for augmenting cancer immunotherapy. Nanoparticles possess versatile attributes, such as prolonged blood circulation, stability, and tumor-targeting capabilities, rendering them ideal for drug delivery. In this review, we elucidate the mechanisms underlying ICD induction and associated therapeutic strategies. Additionally, we provide a concise overview of the immune stress response associated with ICD and explore the potential synergistic benefits of combining ICD induction methods with the utilization of nanocarriers.

Synergistic leaching process for ion-exchange ammonium from weathered crust elution deposited rare earth tailings with potassium magnesium compound eluent.

The ion-exchangeable ammonium (IE-A) that accounts for 60-90% of the total residual ammonium in rare earth tailings has great potential to pollute the surrounding environment, and much research has been done to seek an effective elution method. However, the current study mainly focused on the single salt solution, which made it hard to reach the desired elution efficiency. In this study, the efficient binary compound eluent was prepared, and the response surface experiments and dynamic elution were performed to optimize the elution condition and evaluate the practical application prospect. Batch experimental results showed that the best IE-A elution efficiency could be achieved at the K:Mg molar ratio of 8:2, the liquid-solid ratio of 26:1, and the concentration of 0.1 mol/L at the natural solution pH. Dynamic experimental results indicated that a higher concentration, flow rate, and elution temperature could all accelerate the elution process, and the highest elution efficiency could reach 99%. The fitting results by shrinking core models show that the apparent activation energy of IE-A was 4.24 kJ/mol in the temperature range of 288-328 K, and the reaction order was 0.16. XPS and FTIR revealed that IE-A was effectively eluted by a potassium and magnesium compound leaching agent via an ion-exchange reaction. Overall, the developed compound solution with potassium and magnesium is a candidate for an elution agent that could be used to remove residual ammonium in a closed field of rare earth ores.

Mechanisms of combined bioremediation by phosphate-solubilizing fungus and plants and its effects on cadmium contamination in phosphate-mining wastelands.

Owing to uncontrolled mining activities and lack of ecological protection measures, phosphate-mining wastelands are contaminated with the heavy metal Cd. In this study, Penicillium oxalicum strain ZP6, a Cd-resistant phosphate-solubilizing fungus, was used in combination with the fast-growing, high-biomass plant Brassica juncea L. to enhance Cd remediation in phosphate-mining wastelands. Further, the bioremediation mechanisms were explored and elucidated. In pot experiments, strain ZP6 and Brassica juncea L. alone were significantly effective in removing Cd from phosphate-mining wastelands; however, their combination was more effective, exhibiting a high removal rate of 88.75%. The presence of phosphorite powder increases soil-enzyme activity, promotes plant growth, and reduces the bioaccumulation and translocation factors. However, Cd-inhibited plant growth and chlorophyll content increased malondialdehyde accumulation, which was alleviated by inoculation with strain ZP6. The results from the study indicate that bioremediation using a combination of strain ZP6 and plants is a restoration strategy with appreciable potential to resolve Cd contamination in phosphate-mining wastelands.

PPh3/I2 Promoted Synthesis of Unsymmetrical Disulfides from Sodium Sulfites and 2-Mercaptobenzo Heterocyclics.

A simple and efficient method for the synthesis of unsymmetrical disulfides is reported. Using sodium sulfites and 2-mercaptobenzo heterocyclic compounds as starting materials, the unsymmetrical sulfur-sulfur bonds could be quickly constructed in the PPh3/I2 reaction system under transition-metal-free conditions. This protocol has the advantages of mild reaction conditions, easily available starting materials, and wide substrate scope, showing potential synthetic value for the synthesis of a diversity of biologically or pharmaceutically active compounds.

Environmental impact and optimization suggestions of pig manure and wastewater treatment systems from a life cycle perspective.

With the rapid development of the pig farming industry in China, a large amount of pig manure is inevitably generated. The management and utilization of pig manure in a sustainable approach require a systematic analysis of the environmental impacts generated from the existing pig manure treatment and disposal routes. In this study, three typical pig manure treatment and disposal routes: pig manure solid-liquid separation, i) wastewater biological treatment, direct land application of manure/sludge; ii) black-film anaerobic digestion of wastewater, mono-composting of manure/sludge and land use; iii) wastewater biological treatment, co-composting of manure/sludge and land use, were comparatively assessed in terms of their environmental impacts using the life cycle assessment. The results show that the added chemicals in wastewater treatment and the consumed electricity in composting the manure/sludge are the two main contributors to all environmental impacts. Thus, using green chemicals, controlling the dosage of added chemicals accurately, and selecting composting types with low energy consumption will significantly reduce the environmental burden of pig manure treatment and disposal routes. For the global warming potential of the evaluated three pig manure treatment and disposal routes, direct emissions of greenhouse gases during the composting process contribute the most, accounting for 77 %, 95 %, and 79 %, respectively. Furthermore, the struvite recovery with anaerobic digestion from pig manure will bring excellent environmental benefits, which will markedly offset the toxicity impacts and carbon emissions derived from pig manure treatment and disposal process. Overall, this work quantitatively evaluates the potential environmental impacts of the existing pig manure treatment and disposal routes, providing insights on optimization for future technical improvement and development.

Combining network pharmacology, molecular docking, molecular dynamics simulation, and experimental verification to examine the efficacy and immunoregulation mechanism of FHB granules on vitiligo.

Background: Fufang Honghua Buji (FHB) granules, have proven efficacy against vitiligo in long-term clinical practice. However, its major active chemical components and molecular mechanisms of action remain unknown. The purpose of this study was to confirm the molecular mechanism of FHB's therapeutic effect on vitiligo utilizing network pharmacology, molecular docking, and molecular dynamics simulation prediction, as well as experimental verification. Methods: Traditional Chinese Medicine Systems Pharmacology (TCMSP) and HERB databases were used to obtain the chemical composition and action targets of FHB. Online Mendelian Inheritance in Man (OMIM), DrugBank, DisGeNET, GeneCards, and Therapeutic Target Database (TTD) databases were applied to screen for vitiligo-related targets. Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) enrichment analyses were performed through the Matascape database. Molecular docking and dynamics simulation methods were for the analysis of the binding sites and binding energies between the FHB's active components and the targets. Finally, a vitiligo mouse model was created, and the therapeutic effect and molecular mechanism of action of FHB were validated using enzyme linked immunosorbent assay (ELISA), western blot (WB), and quantitative reverse transcription-polymerase chain reaction (qRT-PCR). Additionally, hematoxylin-eosin staining (HE) and blood biochemical assays were conducted to assess the biosafety of FHB. Result: The screening of chemical composition and targets suggested that 94 genetic targets of FHB were associated with vitiligo. The bioinformatics analysis suggested that luteolin, quercetin, and wogonin may be major active components, and nuclear factor-kappa B p65 subunit (RELA), signal transducer, and activator of transcription (STAT) 3 and RAC-alpha serine/threonine-protein kinase (AKT) 1 may be potential targets of FHB-vitiligo therapy. Molecular docking and dynamics simulation further demonstrated that luteolin, quercetin, and wogonin all bound best to STAT3. Through experimental verification, FHB has been demonstrated to alleviate the pathogenic characteristics of vitiligo mice, suppress the JAK-STAT signaling pathway, reduce inflammation, and increase melanogenesis. The in vivo safety evaluation experiments also demonstrated the non-toxicity of FHB. Conclusions: FHB exerts anti-inflammatory and melanogenesis-promoting effects via the effect of multi-component on multi-target, among which the JAK-STAT pathway is a validated FHB-vitiligo target, providing new ideas and clues for the development of vitiligo therapy.

Advance and Challenges in the Treatment of Skin Diseases with the Transdermal Drug Delivery System.

Skin diseases are among the most prevalent non-fatal conditions worldwide. The transdermal drug delivery system (TDDS) has emerged as a promising approach for treating skin diseases, owing to its numerous advantages such as high bioavailability, low systemic toxicity, and improved patient compliance. However, the effectiveness of the TDDS is hindered by several factors, including the barrier properties of the stratum corneum, the nature of the drug and carrier, and delivery conditions. In this paper, we provide an overview of the development of the TDDS from first-generation to fourth-generation systems, highlighting the characteristics of each carrier in terms of mechanism composition, penetration method, mechanism of action, and recent preclinical studies. We further investigated the significant challenges encountered in the development of the TDDS and the crucial significance of clinical trials.

Treating waste with waste: Adsorption of anionic dyes in wastewater with surfactant-modified phosphogypsum.

Phosphogypsum (PG) is a solid waste generated during the wet process of phosphoric acid production. The environmental-friendly disposal and recycling of PG is vital in the field of environmental solid waste treatment. In this study, PG is used for adsorbent of dyes in wastewater to achieve the goal of recycling waste with waste. Surfactant-modified phosphogypsum (ODBAC@PG) was prepared using octadecyl dimethyl benzyl ammonium chloride (ODBAC) as modifier. ODBAC@PG exhibits high adsorption capability for anionic dyes (methyl blue (MeB) and indocyanine carmine (IC)). The pseudo-second-order kinetic model fits the kinetic experimental data for the adsorption of two organic anionic dyes. Langmuir adsorption isotherm fits the adsorption characteristics of MeB and IC on ODBAC@PG, exhibiting a monolayer adsorption pattern. Thermodynamic parameters indicate the spontaneous and exothermic properties of MeB and IC on ODBAC@PG. MeB and IC have antagonistic effects on each other in binary adsorption system. High adsorption capacity after six cycles of experiments demonstrates the high reusability of ODBAC@PG. The nature for the adsorption includes electrostatic interaction, hydrogen bond and hydrophobic interaction. Using ODBAC@PG for dyes wastewater treatment can accomplish the goal of treating waste with waste and turning waste into treasure.

Performance changes in the anammox process under the stress of rare-earth element Ce(III) and the evolution of microbial community and functional genes.

The high Ce(III) content in ionic rare-earth tailings wastewater has hindered the application of anammox process in this field. Here, the effect of Ce(III) on the performance of anammox processes was investigated, and the evolution of microbial communities and functional genes was explored using metagenomic sequencing. The results showed that the reactor nitrogen removal rate decreased when the Ce(III) concentration reached 25 mg/L, although ammonia nitrogen removal (92.31%) and nitrogen removal efficiency (81.33%) remained at a high level; however, both showed a significant decreasing trend. The relative abundance of anammox bacteria increased continuously from P1-P5, reaching 48.81%, whereas the relative abundance of Candidatus jettenia reached 33.71% at P5, which surpassed that of Candidatus brocadia as the most abundant anammox bacteria, and further analysis of functional genes and metabolic pathways revealed that Candidatus brocadia was richer in biochemical metabolic genes, whereas Candidatus jettenia had richer efflux genes.

The influence of various microplastics on PBDEs contaminated soil remediation by nZVI and sulfide-nZVI: Impedance, electron-accepting/-donating capacity and aging.

The microplastics (MPs) existed in the environment widely has resulted in novel thinking about in-situ remediation techniques, such as nano-zero-valent iron (nZVI) and sulfided nZVI (S-nZVI), which were often compromised by various environmental factors. In this study, three common MPs such as polyvinyl chloride (PVC), polystyrene (PS), and polypropylene (PP) in soil were found to inhibit the degradation rate of decabromodiphenyl ether (BDE209) by nZVI and S-nZVI to different degrees due to MPs inhibiting of electron transfer which is the main way to degrade BDE209. The inhibition strength was related to its impedance (Z) and electron-accepting (EAC)/-donating capacity (EDC). Based on the explanation of the inhibition mechanism, the reason for different aging degrees of nZVI and S-nZVI in different MPs was illustrated, especially in PVC systems. Furthermore, the aging of reacted MPs, functionalization and fragmentation in particular, indicated that they were involved in the degradation process. Moreover, this work provided new insights into the field application of nZVI-based materials for removing persistent organic pollutants (POPs).

Carbon quantum dots (CQDs) mediated Z-scheme g-C3N4-CQDs/BiVO4 heterojunction with enhanced visible light photocatalytic degradation of Paraben.

The construction of a novel Z-scheme system which possesses superior charge separation and high redox ability is highly desirable for efficient photocatalytic degradation of organic pollutants. Herein, a carbon quantum dots (CQDs) modified g-C3N4 (GCN) and BiVO4 (BVO) composite (GCN-CQDs/BVO) was fabricated via an initial loading of CQDs on GCN, and a subsequent combination with BVO during its hydrothermal synthesis. Physical characterization (e.g. TEM, XRD, XPS) verified the intimate heterojunction structure of the composite, while CQDs improved its light absorption. The band structures of GCN and BVO were evaluated, displaying the feasibility for Z-scheme formation. In comparison with GCN, BVO, and GCN/BVO, GCN-CQDs/BVO generated the highest photocurrent and lowest charge transfer resistance, inferring the prominently improved charge separation. Under visible light irradiation, GCN-CQDs/BVO exhibited the significantly enhanced activity in degrading the typical Paraben pollutant--benzyl paraben (BzP), achieving the removal of 85.7% in 150 min. The effects of various parameters were explored, demonstrating that neutral pH was optimal, while coexisting ions (CO32-, SO42-, NO3-, K+, Ca2+, Mg2+) and humic acid impacted the degradation negatively. Meanwhile, trapping experiments and electron paramagnetic resonance (EPR) technique revealed that superoxide radicals (•O2-) and hydroxyl radical (•OH) were primarily responsible for BzP degradation by GCN-CQDs/BVO. In particular, with the assistance of CQDs, the generation of •O2- and •OH was notably augmented. Based on these results, a Z-scheme photocatalytic mechanism was proposed for GCN-CQDs/BVO, where CQDs acted as electron mediators to combine the holes from GCN and electrons from BVO, resulting in significantly improved charge separation and maximized redox ability. Moreover, the toxicity of BzP was remarkably reduced during the photocatalytic process, emphasizing its great potential in abating the risk of Paraben pollutants.