Piezo-electricity, as a unique physical phenomenon, demonstrates high effectiveness in capturing the environmental mechanical energy into polarization charges, offering the possibility to activate the advanced oxidation processes via the electron pathway. However, information regarding the intensification of Fe(VI) through piezo-catalysis is limited. Therefore, our study is the first to apply Bi2WO6 nanoplates for piezo-catalyzation of Fe(VI) to enhance bisphenol A (BPA) degradation. Compared to Fe(VI) alone, the Fe(VI)/piezo/Bi2WO6 system exhibited excellent BPA removal ability, with the degradation rate increased by 32.6% at pH 9.0. Based on the experimental and theoretical results, Fe(VI), Fe(V), Fe(IV) and •OH were confirmed as reaction active species in the reaction, and the increased BPA removal mainly resulted from the enhanced formation of Fe(IV)/Fe(V) species. Additionally, effects of coexisting anions (e.g., Cl-, NO3-, SO42- and HCO3-), humic acid and different water matrixes (e.g., deionized water, tap water and lake water) on BPA degradation were studied. Results showed the Fe(VI)/piezo/Bi2WO6 system still maintained satisfactory BPA degradation efficiencies under these conditions, guaranteeing future practical applications in surface water treatment. Furthermore, the results of intermediates identification, ECOSAR calculation and cytotoxicity demonstrated that BPA degradation by Fe(VI)/piezo/Bi2WO6 posed a diminishing ecological risk. Overall, these findings provide a novel mechanical energy-driven piezo-catalytic approach for Fe(VI) activation, enabling highly efficient pollutant removal under alkaline condition.

The fabrication of low-cost, highly efficient, environmentally friendly, and easily separable metal-free heterogeneous catalysts for environmental remediation remains a challenge. In this study, granular nitrogen-doped highly developed porous carbons with a particle size of 0.25-0.30 mm were prepared by preoxidation and subsequent NH3 modification of a commercially available coconut-based activated carbon, and used to activate peroxymonosulphate (KHSO5) or hydrogen peroxide (H2O2) to degrade bisphenol A (BPA). The nitrogen-doped carbon (ACON-950) prepared by NH3 modification at 950 °C, with the addition of only 0.15 g/L could remove 100% of 50 mg/L BPA in 150 min, and more than 90% of the removed BPA was due to degradation. The removal rates of total organic carbon of ACON-950/KHSO5 and ACON-950/H2O2 systems reached 60.4% and 66.2% respectively, indicating the excellent catalytic activity of ACON-950. The reaction rate constant was significantly positively correlated with the absolute content of pyridinic N (N-6) and graphitic N (N-Q) and negatively and weakly positively correlated with pyrrolic N (N-5) and defects. Quenching experiments combined with electron paramagnetic resonance demonstrated that singlet oxygen was the dominant reactive oxidative species for BPA degradation. ACON-950 was characterized before and after the degradation reaction using N2 adsorption-desorption analyzer, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The results confirmed the prominent contribution of both the N-6 and N-Q to the catalytic performance of nitrogen-doped carbons. The reusability of ACON-950 and its application in actual water bodies further demonstrated its remarkable potential for the remediation of organic pollutants in wastewater.

Bisphenol A (BPA), one of the most widely used plasticizers, is an endocrine-disrupting chemical that is released from plastic products. The aim of this study was to screen and characterize bacteria with excellent BPA-degrading abilities for application in foods. BPA degradation ability was confirmed in 127 of 129 bacterial strains that were isolated from fermented soybean foods. Among the strains, B. subtilis P74, which showed the highest BPA degradation performance, degraded 97.2% of 10 mg/L of BPA within 9 h. This strain not only showed a fairly stable degradation performance (min > 88.2%) over a wide range of temperatures (30-45 °C) and pH (5.0-9.0) but also exhibited a degradation of 63% against high concentrations of BPA (80 mg/L). The metabolites generated during the degradation were analyzed using high-performance liquid chromatography-mass spectrometry, and predicted degradation pathways are tentatively proposed. Finally, the application of this strain to soybean fermentation was conducted to confirm its applicability in food.

Magnetic carbon-based catalysts are promising materials for advanced oxidation processes, offering both high catalytic activity and environmental friendliness, and hold great potential in environmental remediation. In this work, Fe and Co zeolite imidazole frameworks (ZIFs) derived micron-sized magnetic porous carbon beads (MPCBs) were prepared by phase inversion and following the carbonization procedure, and the morphological and structural characteristics of the MPCBs were confirmed. The presence of pores and channels in the MPCBs provides a specific microenvironment for the for the catalysis of the core. Bisphenol A (BPA) was selected for the targeted pollutant, and the catalytic experiments confirmed that the effective catalytic activity of MPCBs in the presence of peroxymonosulfate (PMS), which could almost completely degrade BPA in 20 min with a reaction rate of 0.368 min-1. Furthermore, the MPCBs were used to effectively bacterial inactivation. Intermediate products of the BPA degradation process were validated and the toxicological studies showed a gradual decrease in toxicity, indicating effective reduction of potential hazards. The macroscopic preparation methods we developed for MPCBs that is promising for industrial applications and has the potential to cope with complex environmental remediation.

The information on the collaborative removal of nitrate and trace organic contaminants in the thin-layer capping system covered with Fe-loaded biochar (FeBC) is limited. The community changes of bacteria, archaea and fungi, and their co-occurrence patterns during the remediation processes are also unknown. In this study, the optimized biochar (BC) and FeBC were selected as the capping materials in a batch experiment for the remediation of overlying water and sediment polluted with nitrate and bisphenol A (BPA). The community structure and metabolic activities of bacteria, archaea and fungi were investigated. During the incubation (28 d), the nitrate in overlying water decreased from 29.6 to 11.0 mg L-1 in the FeBC group, 2.9 and 1.8 times higher than the removal efficiencies in Control and BC group. The nitrate in the sediment declined from 5.03 to 0.75 mg kg-1 in the FeBC group, 1.3 and 1.1 times higher than those in Control and BC group. The BPA content in the overlying water in BC group and FeBC group maintained below 0.4 mg L-1 during incubation, signally lower than in the Control group. After capping with FeBC, a series of species in bacteria, archaea and fungi could collaboratively contribute to the removal of nitrate and BPA. In the FeBC group, more metabolism pathways related to nitrogen metabolism (KO00910) and Bisphenol degradation (KO00363) were generated. The co-occurrence network analysis manifested a more intense interaction within bacteria communities than archaea and fungi. Proteobacteria, Firmicutes, Actinobacteria in bacteria, and Crenarchaeota in archaea are verified keystone species in co-occurrence network construction. The information demonstrated the improved pollutant attenuation by optimizing biochar properties, improving microbial diversity and upgrading microbial metabolic activities. Our results are of significance in providing theoretical guidance on the remediation of sediments polluted with nitrate and trace organic contaminants.

Peracetic acid is an emerging oxidant and disinfectant for wastewater purification. In this study, we first developed a comprehensive and accurate model to elucidate the reaction mechanisms and simulate reaction kinetics of peracetic acid (PAA, CH3C(=O)OOH) activated by chloride (Cl-) based on experimental results and literature. A diversity of experiments methods (e.g., quenching experiments, probe compounds degradation, electron paramagnetic resonance (EPR) measurements) and kinetic modeling were used to determine the reactive species. As a result, carbon-centered radicals and free chlorine reactive species (Cl2 and HClO) were devoted to BPA degradation in the PAA/Cl- system. The carbon-centered radicals CH3C(=O)OO•, CH3C(=O)O•, CH3OO•, and •CH3 greatly accelerated BPA degradation with their corresponding kinetics of kCH3C(=O)OO•, BPA = 2 × 108 M-1 s-1, kCH3C(=O)O•, BPA = 2 × 107 M-1 s-1, k•CH3, BPA = 2 × 106 M-1 s-1 and kCH3OO•, BPA = 2 × 104 M-1 s-1. Dissolved Cl2(l) species was also important for BPA degradation with kCl2, BPA of 2 × 107 M-1 s-1, much higher than HClO/ClO- of kHClO, BPA = 1.2 × 101 M-1 s-1 and kClO-, BPA = 9 × 10-3 M-1 s-1. While free chlorine tends to transform BPA to estrogenic chlorinated organic products, the primary degradation of BPA by carbon-centered radicals results in chlorine-free products, reducing the production of disinfection byproducts during the treatment of saline wastewater. This study improves the knowledge of reaction kinetics and mechanism and reactive species generation in the PAA/Cl- system.

Bioelectrochemical systems (BESs) with integrated photoactive components have been shown to be a promising strategy for enhancing the performance for bioenergy generation and pollutant removal. This study revealed an efficient photo-BES with an enhanced pollutant degradation rate by utilizing self-produced biomolecules as photosensitizers in situ. Results showed that the BES could increase the coulombic efficiency from 60.8% to 73.0% and the degradation rate of bisphenol A (BPA) from 0.030 to 0.189 h-1 when the suspension in the reactor was illuminated with simulated sunlight in the absence of any external photosensitizers. We identified that the regular BES released many organic substances into the reactor during operation. These substances, including dissolved biomolecules and solid cell residues, were photoactive for producing hydroxyl radicals during light illumination. Quenching experiments verified that the •OH generated from the self-produced biophotosensitizers contributed to the enhanced degradation of BPA. Additionally, the phototransformation of biophotosensitizers was also observed in photo-BES. The quantity of tyrosine protein-like components decreased, but that of the humic components remained relatively stable. Our findings imply that BESs with integrated self-produced biophotosensitizers may be promising for constructing advanced electrochemical and biological systems for synchronous bioelectricity production and degradation of organic pollutants in wastewater treatments.

Photocatalysis provides an impetus for the synergetic removal of Cr(VI) and organic contaminants, but the generation of Cr intermediates and their potential oxidizability may be overlooked in pollutant conversion. Herein, the Cr intermediates in the Cr(VI) reduction process were emphasized in Cr(VI)/bisphenol A (BPA) by using graphitic carbon nitride as a photocatalyst. The active species for BPA photodegradation in the BPA system and Cr(VI)/BPA system suggested that the Cr(VI) reduction process indeed promotes BPA photodegradation. Electron paramagnetic resonance (EPR) of Cr complexes and in situ variable-temperature EPR analysis demonstrated Cr(V) intermediate (g = 1.978) generation in Cr(VI) reduction and its oxidization for BPA degradation in photocatalysis. By adding the electron donor Na2SO3, BPA degradation was induced in Cr(VI)/BPA solution, further confirming the positive effect of Cr(V). Moreover, the difference in BPA degradation products in the BPA/air, Cr(VI)/BPA/air, and Cr(VI)/BPA/Ar systems indirectly explained why the Cr(V) intermediate was involved in BPA degradation. Density functional theory calculations revealed that photogenerated electrons can reduce the free energy (0.98 eV) of converting Cr(VI) into Cr(V), which can facilitate the subsequent Cr(V) oxidation step for BPA degradation. This work contributes to the exploration of the Cr(VI) reduction process and the synergistic removal of organic pollutants in Cr(VI)/organics systems.

The slow redox rate of Fe(III)/Fe(II) couples is a rate-limiting step for Fenton-like performance of Fe-MOFs. In this study, a series of catalysts (MIL-101) with various p-phthalic acid/2-aminoterephthalic acid (H2BDC/NH2-H2BDC) molar ratios were prepared using a simple and mild chemical method and applied for catalyzed degradation of bisphenol A (BPA). Interestingly, the -NH2 modified MIL-101(Fe) can adjust Fe-Oxo node by increasing the electron density of Fe(III) in the presence of -NH2 group with high electron density, thus forming Fe(II) in situ in MOFs. Meanwhile, the -NH2 groups used as electron-donors can promote electron transfer, resulting in faster Fe(III)→Fe(II) half-reaction and active H2O2 to continuously generate •OH radical. The BPA degradation and rate constant of Fe-BDC-NH2/H2O2 system are 15.4-fold and 86.8-fold higher than that of Fe-BDC/H2O2 system, respectively. The density functional theory (DFT) calculations showed that Fe-BDC-NH2 possesses higher Fermi level energy (-4.88 eV) and lower activation energy barriers (0.32 eV) compared with Fe-BDC. Moreover, Fe-BDC-NH2 showed good reusability and stability. This work offers a highly efficient and stable MOFs-based Fenton-like catalyst to rapidly degrade organic pollutants over a wide pH range for potential applications in wastewater treatment.

Bisphenol (BPA) is a key ingredient in the production of epoxy resins and some types of plastics, which can be released into the environment and alter the endocrine systems of wildlife and humans. In this study, the ability of the fungus M. roridumIM 6482 to BPA elimination was investigated. LC-MS/MS analysis showed almost complete removal of BPA from the growth medium within 72 h of culturing. Products of BPA biotransformation were identified, and their estrogenic activity was found to be lower than that of the parent compound. Extracellular laccase activity was identified as the main mechanism of BPA elimination. It was observed that BPA induced oxidative stress in fungal cells manifested as the enhancement in ROS production, membranes permeability and lipids peroxidation. These oxidative stress markers were reduced after BPA biodegradation (72 h of culturing). Intracellular proteome analyses performed using 2-D electrophoresis and MALDI-TOF/TOF technique allowed identifying 69 proteins in a sample obtained from the BPA containing culture. There were mainly structural and regulator proteins but also oxidoreductive and antioxidative agents, such as superoxide dismutase and catalase. The obtained results broaden the knowledge on BPA elimination by microscopic fungi and may contribute to the development of BPA biodegradation methods.