COF-derived porous nitrogen-doped carbon for removal of emerging organic contaminants and efficient uranium extraction from seawater.

The development of adsorbents for efficient and highly selective seawater extraction of uranium was instrumental in fostering sustainable progress in energy and addressing the prevailing energy crisis. However, the complex background composition of the marine environment, including radionuclides, organic pollutants, and a large number of co-existing heavy metal ions, were non-negligible obstacles to the extraction of uranium from seawater. The present investigation successfully employed a self-templated approach to synthesize porous nitrogen-doped carbon (PNC) derived from COF, which exhibited tremendous potential as an adsorbent for pollutant removal in environmental treatment. LZU1@PNC not only retained the structural features of the original COF-LZU1, but also overcame the acid-base instability problem commonly found in COFs. Subsequently, the removal process of two typical water pollutants on the material was investigated using 2,4-DCP and [UO2(CO3)3]4-. The results demonstrated that LZU1@PNC exhibited superior removal performance for the target pollutants compared to COF-LZU1, owing to its larger specific surface area and abundant defect structure. After six desorption-regeneration cycles, LZU1@PNC still maintained a high removal rate of the target contaminants, demonstrating the stability of this material and its excellent recyclability. In addition, based on various characterization techniques, the removal mechanism of 2,4-DCP was presumed to be mainly electrostatic attraction, hydrogen bonding, and π-π stacking interactions. Conversely, the elimination process of [UO2(CO3)3]4- predominantly relied on surface complexation phenomena. The present investigation provided new perspectives and stimulated a broader study of other COF-derived carbon materials and their modifications as adsorbents for uranium extraction from seawater and other applications.

Adsorption and photocatalytic degradation of 2,4-dicholrophenol using surgical mask derived SMAC-Fe2O3 composite; adsorption isotherms, kinetics, thermodynamics.

Hybrid material of surgical mask activated carbon (SMAC) and Fe2O3 (SMAC-Fe2O3) composite was prepared by simple co-precipitation method and used as potential material for the remediation of 2,4-dicholrophenol (2,4-DCP). The XRD patterns exhibited the presence of SMAC and Fe2O3, FTIR spectrum showed the FeO-carbon stretching at the wavenumber from 400 to 550 cm-1. UV-Vis DRS results showed the band gap was 1.97 eV and 2.05 eV for SMAC-Fe2O3 and Fe2O3, respectively. The SEM images revealed that the Fe2O3 doped onto the fiber morphology of SMAC. The outcomes of the BET examination exhibited a surface area of 195 m2/g and a pore volume of 0.2062 cm3/g for the SMAC/Fe2O3 composite. The batch mode study shows the maximum adsorption and photocatalytic degradation efficacies which were 97% and 78%, respectively. The experimental data was studied with both linear and nonlinear adsorption isotherm and kinetics models. The nonlinear Langmuir isotherm and pseudo-second-order kinetics (PSOK) models have well fit compared with other models. The Langmuir maximum adsorption capacity (qmax) was found 161.60 mg/g. Thermodynamic analysis shows that the 2,4-DCP adsorption onto SMAC-Fe2O3 was a spontaneous and exothermic process. The PSOK assumes that the adsorption process was chemisorption. The photocatalytic degradation rate constant of 2,4-DCP was calculated using pseudo-first-order kinetics (PFOK) and the rate constant for SMAC-Fe2O3 and Fe2O3 were 0.859 × 10-2 min-1 and 0.616 × 10-2 min-1, correspondingly. In addition, the obtained composite exhibited good reusability after a few cycles. These results confirmed that SMAC-Fe2O3 composite is an effective adsorbent and photocatalyst for removing 2,4-DCP pollutants.

Natural Attenuation of 2,4-Dichlorophenol in Fe-Rich Soil during Redox Oscillations: Anoxic-Oxic Coupling Mechanism.

Natural attenuation of organic contaminants can occur under anoxic or oxic conditions. However, the effect of the coupling anoxic-oxic process, which often happens in subsurface soil, on contaminant transformation remains poorly understood. Here, we investigated 2,4-dichlorophenol (2,4-DCP) transformation in Fe-rich soil under anoxic-oxic alternation. The anoxic and oxic periods in the alternating system showed faster 2,4-DCP transformation than the corresponding control single anoxic and oxic systems; therefore, a higher transformation rate (63.4%) was obtained in the alternating system relative to control systems (27.9-42.4%). Compared to stable pH in the alternating system, the control systems presented clear OH- accumulation, caused by more Fe(II) regeneration in the control anoxic system and longer oxygenation in the control oxic system. Since 2,4-DCP was transformed by ion exchangeable Fe(II) in soil via direct reduction in the anoxic process and induced ·OH oxidation in the oxic process, OH- accumulation was unbeneficial because it competed for proton with direct reduction and inhibited •OH generation via complexing with Fe(II). However, the alternating system exhibited OH--buffering capacity via anoxic-oxic coupling processes because the subsequent oxic periods intercepted Fe(II) regeneration in anoxic periods, while shorter exposure to O2 in oxic periods avoided excessive OH- generation. These findings highlight the significant role of anoxic-oxic alternation in contaminant attenuation persistently.

Effects of 2,4-dichlorophenol on non-specific immunity, histopathological lesions, and redox balance in African Catfish, clarias gariepinus (Burchell, 1822).

The toxic effects of 2, 4-dichlorophenol (2, 4-DCP) on aquatic organisms are well-established; however, the details regarding the mechanisms underlying the toxicity, especially immunotoxicity are poorly understood. Consequently, the aim of this study was to investigate the histopathologic, oxidative stress and immunotoxic effects attributed to exposure to sublethal concentrations of 2,4-DCP in the African catfish, Clarias gariepinus. Juvenile C. gariepinus were exposed to 0.4, 0.8, or 1.6 mg/L 2, 4-DCP for 28 days after which blood and head kidney were extracted for the determination of various nonspecific innate immune parameters while the liver was excised for histopathology examination and measurement of oxidative stress biomarkers. Control fish were maintained in water spiked 10 µL/L ethanol, representing the solvent control. A significant increase was noted in the activities of lactate dehydrogenase and superoxide dismutase as well as in levels of lipid peroxidation and DNA fragmentation in a dose-dependent manner, with higher adverse effects observed at the highest concentration tested (1.6 mg/L). The total white blood cells (WBC) count was significantly elevated in fish exposed to 2,4-DCP compared to control. Myeloperoxidase content was decreased significantly in fish exposed to 2,4-DCP especially at the highest concentration (1.6 mg/L) compared to controls. The respiratory burst activity did not differ markedly amongst groups. Histopathological lesions noted included edema, leucocyte infiltration, and depletion of hemopoietic tissue in the head kidney of exposed fish. There was significant upregulation in the mRNA expression of tumor necrosis factor (TNF-α) and heat shock protein 70 (HSP 70) but downregulation of major histocompatibility complex 2 (MHC 2) in exposed fish. Data demonstrated that exposure to 2,4-DCP resulted in histopathological lesions, oxidative stress, and compromised immune system in C. gariepinus.

Association between DCP levels and kidney stone prevalence in US female adults based on NHANES data.

Our study aimed to evaluate the correlation between levels of 2,4-DCP(2,4-Dichlorophenol) and 2,5-DCP(2,5-Dichlorophenol) and the prevalence of kidney stones in US female adults. Participants were chosen from the National Health and Nutrition Examination Survey database, spanning the years 2007-2016. Dose-response curves were analyzed using logistic regression, subgroup analyses, and other statistical methods to evaluate the relationship between 2,4-DCP and 2,5-DCP levels and the prevalence of kidney stones. The final study included 3220 participants aged over 20 years, with 252 females reporting a history of kidney stones. After accounting for all interfering variables, we found that every 0.1 ug/ml increase in 2.4-DCP correlated with a 1% rise in kidney stone prevalence (OR = 1.01, 95% CI 1.00, 1.01), whereas the same increase in 2.5-DCP was linked to a 27% growth in prevalence (OR = 1.27, 95% CI 1.01, 1.61). Sensitivity analysis was performed by triangulating 2,4-DCP and 2,5-DCP levels. The dose-response curves demonstrated a linear positive relationship between 2,4-DCP and 2,5-DCP levels and the risk of stone development. Our findings indicate a positive correlation between 2,4-DCP and 2,5-DCP levels and the prevalence of kidney stones in US female adults. This association is of clinical significance; however, a direct causal relationship cannot be definitively established.

Cyanobacterial degradation of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D): Its response to the oxidative stress induced by the primary degradation product 2,4-dichlorophenol (2,4-DCP).

Excessive use of herbicides in agricultural fields has become a major environmental concern due to the negative effects on the ecosystem. Microbial degradation has been well-known as an effective approach for combating such non-natural substances in soil. In the present study, the degradation of 2,4-Dichlorophenoxyacetic acid (2,4-D) as a result of metabolic activities of a cyanobacterium Nostoc muscorum Meg 1 was investigated using GC-MS analysis. After seven days of 2,4-D exposure, the main residue obtained was 2,4-dichlorophenol (2,4-DCP) at RT: 8.334 (confirmed using NIST library). The effects of 2,4-DCP were studied in a cyanobacterium Nostoc muscorum Meg 1 isolated from a rice field where 2,4-D is commonly used. Exposure to 2,4-DCP at 20, 40, and 80 ppm significantly increased ROS production in the cyanobacterium by 74, 107, and 211 % (p < 0.001). With rising 2,4-DCP concentrations in the surroundings, lipid peroxidation and protein oxidation in the organism correspondingly increased, indicating cellular injury. The mRNA and protein contents, and also the activities of different oxidant neutralizing enzymes such as CAT, SOD, GR, and GPx and the non-enzymatic antioxidants (proline, GSH, thiol and phytochelatin content) were found augmented in 20 ppm 2,4-DCP exposed cultures. However, in the presence of 40 and 80 ppm 2,4-DCP, most enzymatic and non-enzymatic antioxidants were severely compromised. At higher exposures, the organism's attempt to mitigate the oxidants was still visible, as both proline and TSH levels increased. SEM and TEM analysis aided in visualizing the effects of 2,4-DCP on the morphology and ultrastructures of the organism.

Degradation of 2,4-DCP by immobilized laccase on modified biochar carrier.

Rape straw was used as the raw material for the biochar in this study, which was then changed using acid, alkali, and magnetic techniques. The laccase was attached using the adsorptions-crosslinking process, and the three modified biochars served as the carriers. The ideal circumstances for laccase immobilization were explored, and both biochar and immobilized laccase's characteristics were examined. The removal of 2,4-dichlorophenol (2,4-DCP) by immobilized laccase from modified biochar and its degradation products were researched. The main conclusions are as follows: the optimal concentration of glutaraldehyde (GLU) was 4%, and the pH was four, and the enzyme dosage was 1.75 mg/mL for the immobilized laccase of acid-modified biochar (SBC@LAC). The optimal concentration of GLU was 5%; the pH was four, and the enzyme dosage was 2 mg/mL for immobilized laccase from alkali-modified biochar (JBC@LAC). The optimal concentration of GLU was 5%; the pH was four, and the enzyme dosage was 1.75 mg/mL for immobilized laccase from magnetically modified biochar (CBC@LAC). SEM images could show the changes in the surface morphology of biochar caused by three modification methods. The BET results demonstrated that acid and magnetic modification increased the specific surface area of biochar, and alkali modification mainly expanded the pore size of biochar. FT-IR and XRD showed that modification and laccase loading had little effect on the structure of biochar. The stability of immobilized laccase was better than that of free laccase in acid-base, heat, and storage. Among the three modified biochar immobilized laccases, JBC@LAC showed the best acid-base stability and thermal stability, and the relative enzyme activity changed the least when pH and temperature conditions changed. The storage stability of SBC@LAC is the best. After 30 days of storage, the relative enzyme activity is still 83%. The removal rates of 2,4-DCP were 57, 99, and 63%, respectively, by SBC@LAC, JBC@LAC, and CBC@LAC. After five reuses, the removal rates of 2,4-DCP by SBC@LAC, JBC@LAC and CBC@LAC were 26, 42, and 27%, respectively. The intermediate products of 2,4-DCP degradation by immobilized laccase were p-phenol, p-benzoquinone and maleic acid.

The reaction pathway and mechanism of 2,4-dichlorophenol removal by modified fly ash-loaded nZVI/Ni particles.

Nanoscale zero-valent iron (nZVI) is more valuable in environmental restoration than other materials. Chemical treatment of fly ash (CFA) was employed as a support material to disperse iron nickel bimetal nanoparticles (CFA-nZVI/Ni) to remove 2,4-dichlorophenol (2,4-DCP). Batch experiments showed that 2,4-DCP was completely removed by CFA-nZVI/Ni, and an optimal loading ratio was 8:1. The degradation of 2,4-DCP by CFA-nZVI/Ni was a chemical control reaction with an activation energy of 95.6 kJ mol-1 and followed pseudo-first-order kinetics. The addition of Cl- increased the removal rate of 2,4-DCP by 4%, while the addition of CO32- and SO42- decreased the removal rate of 2,4-DCP by 32% and 72.3%, respectively. The removal process of 2,4-DCP by CFA-nZVI/Ni included adsorption and reduction. The 2-CP (7.1 mg/L) and 4-CP (11.6 mg/L) could be converted to phenol using the CFA-nZVI/Ni system. Cl on the para-position of 2,4-DCP was simpler to remove than on the ortho-position. The following steps were taken in the electrophilic substitution reaction between substituted phenols and hydrogen radicals: 2,4-DCP > 2-CP > 4-CP > phenol. This research provides a novel concept to effectively remove 2,4-DCP and mechanism analysis.

Mesoporous Polymeric Ionic Liquid via Confined Polymerization for Laccase Immobilization towards Efficient Degradation of Phenolic Pollutants.

Laccase immobilization is a promising method that can be used for the recyclable treatment of refractory phenolic pollutants (e.g., chlorophenols) under mild conditions, but the method is still hindered by the trade-off limits of supports in terms of their high specific surface area and rich functional groups. Herein, confined polymerization was applied to create abundant amino-functionalized polymeric ionic liquids (PILs) featuring a highly specific surface area and mesoporous structure for chemically immobilizing laccase. Benefiting from this strategy, the specific surface area of the as-synthesized PILs was significantly increased by 60-fold, from 5 to 302 m2/g. Further, a maximum activity recovery of 82% towards laccase was recorded. The tolerance and circulation of the immobilized laccase under harsh operating conditions were significantly improved, and the immobilized laccase retained more than 84% of its initial activity after 15 days. After 10 cycles, the immobilized laccase was still able to maintain 80% of its activity. Compared with the free laccase, the immobilized laccase exhibited enhanced stability in the biodegradation of 2,4-dichlorophenol (2,4-DCP), recording around 80% (seven cycles) efficiency. It is proposed that the synergistic effect between PILs and laccase plays an important role in the enhancement of stability and activity in phenolic pollutant degradation. This work provides a strategy for the development of synthetic methods for PILs and the improvement of immobilized laccase stability.

Reconstruction of microbiome and functionality accelerated crude oil biodegradation of 2,4-DCP-oil-contaminated soil systems using composite microbial agent B-Cl.

Biodegradation is one of the safest and most economical methods for the elimination of toxic chlorophenols and crude oil from the environment. In this study, aerobic degradation of the aforementioned compounds by composite microbial agent B-Cl, which consisted of Bacillus B1 and B2 in a 3:2 ratio, was analyzed. The biodegradation mechanism of B-Cl was assessed based on whole genome sequencing, Fourier transform infrared spectroscopy and gas chromatographic analyses. B-Cl was most effective at reducing Cl- concentrations (65.17%) and crude oil biodegradation (59.18%) at 7 d, which was when the content of alkanes ≤ C30 showed the greatest decrease. Furthermore, adding B-Cl solution to soil significantly decreased the 2,4-DCP and oil content to below the detection limit and by 80.68%, respectively, and reconstructed of the soil microbial into a system containing more CPs-degrading (exaA, frmA, L-2-HAD, dehH, ALDH, catABE), aromatic compounds-degrading (pcaGH, catAE, benA-xylX, paaHF) and alkane- and fatty acid-degrading (alkB, atoB, fadANJ) microorganisms. Moreover, the presence of 2,4-DCP was the main hinder of the observed effects. This study demonstrates the importance of adding B-Cl solution to determine the interplay of CPs with microbes and accelerating oil degradation, which can be used for in-situ bioremediation of CPs and oil-contaminated soil.

Persulfate activation by sludge-derived biochar for efficient degradation of 2,4-dichlorophenol: performance and mechanism.

Porous sludge biochar (PSDBC) and zero-valent iron (ZVI) supported on porous sludge biochar composite (ZVI@PSDBC) were synthesized using municipal sludge through pyrolysis under N2 atmosphere, which manifested upgraded performance in persulfate (PS) activation for 2,4-dichlorophenol (2,4-DCP) degradation. The 2,4-DCP (50 mg/L) could be almost completely removed within 20 min under relatively low PS dosage (0.5 mmol/L) in both PSDBC/PS and ZVI@PSDBC/PS systems, and the mineralization rate could respectively approach 73.7% and 91.6% in 60 min. Combined with a scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) characterization and electron spin-resonance (ESR) detection, electrochemical analysis, the radical and non-radical pathways in the catalytic systems were discussed. Graphitized structure and superior conductivity made PSDBC and ZVI@PSDBC not only act as electron donors in PS activation to create radicals (mainly SO4·- and ·OH), but also as "mediators" to facilitate the direct electron transfer from 2,4-DCP to the catalysts-PS complexes. The C=O groups of PSDBC and ZVI@PSDBC aided in the production of 1O2. Meanwhile, zero-valent iron nanoparticles promoted the formation of radicals as the reactive sites of PS, resulting in the most effective 2,4-DCP degradation in the ZVI@PSDBC/PS system. The stability and practicability of sludge biochar materials had been demonstrated in reusability and actual wastewater experiments. The findings provided a promising way for the reuse of municipal sludge and effective PS activation in wastewater treatment.

Degradation of 2,4-Dichlorophenol by Nitrilotriacetic acid-modified photo-Fenton system: effects of organic and inorganic factors.

It has proved that the photo-Fenton system modified by polycarboxylic acid is effective against the degradation of organic pollutants. Still, its effect and impact on actual water bodies are not clear. Therefore, this study mainly discussed the effect of actual water elements on the degradation of 2,4-Dichlorophenol in photo-Fenton system modified by Nitrilotriacetic acid (NTA) and its mechanism in pure water. The specific research contents were: the effect of initial concentration of 2,4-Dichlorophenol on its degradation efficiency; the effect of organic matters on the degradation of 2,4-Dichlorophenol; the effect of cations and anions; the effect of different actual water bodies. And the main results were as follows: In the effect of initial concentration, when the concentration of 2,4-Dichlorophenol was 20 mg·L-1, the degradation efficiency was the best (reached 100%). But, with the increase of initial concentration, the degradation efficiency of the system became worse and worse; the coexistence of the same kind of organic compounds can inhibit each other's degradation, and the degradation rate of pollutants in the mixed system was slower than that in the single system; the addition of anions and cations inhibited the degradation of 2,4-Dichlorophenol, and the degradation efficiency varied with the concentration of ions, in which the effect of anions was more complex; the degradation efficiency of 2,4-Dichlorophenol in three kinds of actual water bodies was lower than in deionized water, especially in PPMW. However, the degradation rates of DSTP and NLW were the fastest in the first 20 min.

2,4-Dichlorophenol Increases Primordial Germ Cell Numbers via ESR2a-Dependent Pathway in Zebrafish Larvae.

Previous studies have reported the feminizing effects of 2,4-dichlorophenol (2,4-DCP) on zebrafish (Danio rerio). However, the effect of 2,4-DCP on the number of primordial germ cells (PGCs), an indicator for early sex differentiation, remains elusive. In the present study, Tg (piwil1:egfp-UTR nanos3) zebrafish (GFP-labeled PGCs) were treated with 2,4-DCP (10, 20, and 40 µg/L) from 5 to 15 days postfertilization to explore the effect on PGC numbers and to elucidate associated molecular mechanisms. The results showed that 2,4-DCP exposure increased PGC numbers, as evidenced by larger GFP fluorescent areas, upregulated expressions of PGC marker genes (vasa and dnd), and raised the female ratio. Notably, the mRNA level of estrogen receptor 2a (esr2a) was also increased subsequently. Moreover, docking studies revealed stable 2,4-DCP interactions with ESR2a, speculating a role of ESR2a signaling pathway in 2,4-DCP toxicity. Furthermore, in esr2a knockout (esr2a-/-) zebrafish, the effects of 2,4-DCP were considerably minimized, proving the involvement of the ESR2a signaling pathway in the 2,4-DCP-mediated increase in PGC numbers. Dual-luciferase reporter gene assay and point mutation studies demonstrated that 2,4-DCP-stimulated promoter activity was mediated by estrogen response element (ERE) located in -686/-674 of the vasa promoter and -731/-719 of the dnd promoter. Overall, 2,4-DCP can potentially enhance the expression of vasa and dnd by binding to zebrafish ESR2a, thus leading to increased PGC numbers and subsequent female-biased sex differentiation.

Degradation of 2,4-DCP by the immobilized laccase on the carrier of sodium alginate-sodium carboxymethyl cellulose.

In this paper, sodium alginate-sodium carboxymethyl cellulose (SA-CMC) composite material was used as a carrier, and sodium alginate-embedded laccase (Lac@SC) was prepared by traditional embedding method. After that, ethylene glycol diglycidyl ether (EGDE) and glutaraldehyde (GLU) were used as cross-linking agents, two different cross-linking-embedded co-immobilized laccases (Lac@SCG and Lac@SCE) were innovatively prepared, respectively, and then these immobilized laccases were characterized by SEM, FT-IR and XRD, and the stability of the three immobilized laccases was explored. In addition, the effects of different factors on the removal of 2,4-DCP by immobilized laccase were studied, and the degradation kinetic models of three immobilized laccases on 2,4-DCP were summarized, the possible degradation pathways of pollutants were also given. Experimental results showed that compared to free laccase, the pH stability, thermal stability and storage stability of immobilized laccase were greatly improved. These immobilized laccases could maintain high activity at pH3~6, 45~55 °C. Lac@SCG had the best storage stability. After 30 days of storage, the relative enzyme activity was still more than 40%. Lac@SC had good reusability, the relative enzyme activity was still more than 50% after 5 uses. In the degradation of 2,4-DCP, all three immobilized laccases showed good performance, when Lac@SCE was at pH5, 35 °C, 25 h, the removal rate of 2,4-DCP could reach 95.2%; When at 45 °C, Lac@SC had the highest degradation rate which reach to 94%; At 45 °C, the degradation rate of Lac@SCG reached 83.2%.

Vertically grown CeO2 and TiO2 nanoparticles over the MIL53Fe MOF as proper band alignments for efficient H2 generation and 2,4-DCP degradation.

The design of highly efficient photoca talysts for clean energy production and environmental remediation are the grand challenges of scientific research. Herein, TiO2@MIL53Fe and CeO2@MIL53Fe composite photocatalysts are synthesized via solvothermal technique. The SEM and TEM micrographs reveal that TiO2 and CeO2 nanoparticles are vertically grown onto the surface of MIL53Fe MOF. Further, HRTEM micrograph confirmed the formation of heterojunction. It has been investigated that the resultant TiO2@MIL53Fe and CeO2@MIL53Fe photocatalysts exhibit remarkably improved visible light activities for H2 production and 2,4-dichlorophenol (2,4-DCP) degradation in comparison to the bare MIL53Fe photocatalyst. The enhanced photoactivities of the fabricated TiO2@MIL53Fe and CeO2@MIL53Fe photocatalysts are attributed to significantly promoted charge separation as confirmed via the surface photo voltage (SPV) and photoluminescence (PL) results. Further, the photocatalysts exhibit high stability and reusability as confirmed via the recyclable tests. This work will promote the design of MOF-based efficient photocatalysts for clean energy production and environment purification.

Degradation of 2,4-dichlorophenol by cathodic microarc plasma electrolysis: characteristics and mechanisms.

In this work, we used cathodic microarc plasma electrolysis (CMPE) to degrade 2,4-dichlorophenol (2,4-DCP) in simulated wastewater. By investigating and comparing the removal efficiencies and chemical oxygen demand (COD) during the degradation process, higher bath voltage and alkaline condition were considered as more suitable for the 2,4-DCP decomposition. Higher initial 2,4-DCP concentration was attributed to the increase in the utilisation of the energy input. The plasma characteristics during CMPE were studied by optical emission spectroscopy (OES). It was found that the 2,4-DCP directly participated in the plasma discharge process. Furthermore, by studying the evolution of intermediate products at different experimental parameters, it was found that the existence of Cl- played an important role in the opening of benzene ring, which activated the ortho-substitutions of hydroxyl, meanwhile accelerated the p-substitutions. The instantaneous high temperature and high pressure and the Cl- that were generated and driven by cathodic plasma made the decomposition of 2,4-DCP much quicker.

Reactive oxygen species formation driven by acidophiles mediated pyrite oxidation and its potential role on 2,4-dichlorophenol transformation.

Researches of reactive oxygen species (ROS) generation from pyrite oxidation and its impact on contaminants transformation has been constrained to abiotic conditions. However, pyrite oxidation by acidophiles is widespread in acidic environments. The potential role of these microorganisms on pyrite-induced ROS formation and pollutants processing is not understood well. Here, ROS production and 2,4-DCP transformation during pyrite oxidation under oxic and anoxic atmospheres by Acidithiobacillus ferrooxidans (A. ferrooxidans) were explored. 2,4-DCP removal was enhanced in biosystem. Under oxic and anoxic conditions, microbially mediated pyrite oxidation resulted in removing 93.66% and 43.77% 2,4-DCP, which were 1.14- and 1.51-fold greater than that without cells. Based on intermediates identified by LC-MS, the transformation pathway of 2,4-DCP was proposed. The trapping experiments demonstrated ROS contributed during 2,4-DCP transformation. The improving effect of A. ferrooxidans on 2,4-DCP degradation was mainly due to ROS increase. A. ferrooxidans was to promote pyrite surface renew, exposing more Fe(II) and Fe(III) sites that facilitated O2 reduction and H2O dissociation for ROS generation. Biogenic ROS and sulfite bio-oxidation with the free radical mechanism provided other ROS sources. ESR revealed A. ferrooxidans-pyrite interaction led to sustainable ROS production, indicating it could be a significant pathway in driving geochemical cycles of elements.

Visible light photodegradation of 2,4-dichlorophenol using nanostructured NaBiS2: Kinetics, cytotoxicity, antimicrobial and electrochemical studies of the photocatalyst.

Removal of the hazardous and endocrine-disrupting 2,4-dichlorophenol (2,4-DCP) from water bodies is crucial to maintain the sanctity of the ecosystem. As a low bandgap material (1.37 eV), NaBiS2 was hydrothermally prepared and used as a potential photocatalyst to degrade 2,4-DCP under visible light irradiation. NaBiS2 appeared to be highly stable and remained structurally undeterred despite thermal variations. With a surface area of 6.69 m2/g, NaBiS2 has enough surface-active sites to adsorb the reactive molecules and exhibit a significant photocatalytic activity. In alkaline pH, the adsorption of 2,4-DCP on NaBiS2 appeared to decrease whereas, the acidic and neutral environments favoured the degradation. An increase in the photocatalyst dosage enhanced the degradation efficiency from 81 to 86 %, because of higher vacant adsorbent sites and the electrostatic attraction between NaBiS2 and 2,4-DCP. The dominant scavengers degraded 2,4-DCP by forming a coordination bond between chlorine's lone pair of electrons and the vacant orbitals of bismuth, following the order hole> OH > singlet oxygen. Being non-toxic to both natural and aquatic systems, NaBiS2 exhibits antifungal properties at higher concentrations. Finally, the electron-rich NaBiS2 is an excellent electrocatalyst that effectively degrades organic pollutants and is a promising material for industrial and environmental applications.

Laccase immobilized on amino-functionalized magnetic Fe3O4-SiO2 core-shell material for 2,4-dichlorophenol removal.

In this study, an amino-functionalized magnetic silica microsphere material (Fe3O4-SiO2-NH2) was prepared. Using glutaraldehyde as a cross-linking agent, Trametes versicolor laccase was adsorbed-covalently bonded and immobilized on the material to prepare Laccase @ Fe3O4-SiO2. In addition, the materials were characterized and analysed by SEM, TEM, XRD, FT-IR and VSM. Finally, the thermal inactivation dynamics of immobilized laccase in polar/non-polar/toxic systems and the adsorption and degradation of 2,4-DCP were studied. The results showed that Laccase @ Fe3O4-SiO2 under the optimal conditions (pH 6, temperature 65°C, initial concentration of 2,4-DCP 10 mg/L), the removal rate was as high as 81.6%. Moreover, compared with free laccase, immobilized laccase had good tolerance under low pH and high-temperature conditions, and storage stability was also greatly improved. After repeated use for 7 times, Laccase @ Fe3O4-SiO2 can still maintain 59% removal rate of 2,4-DCP, which gives it the potential for industrial applications.

Degradation of 2,4-DCP using persulfate and iron/E-carbon micro-electrolysis coupling system.

The greenhouse gas carbon dioxide (CO2) was converted to a novel CO2 conversion material (electrolytic carbon, EC) by molten salt electrochemical conversion, which served as the carbon source to prepare an iron-carbon composite (Fe-EC). The composite was used to activate persulfate (PS) and degrade 2,4-dichlorophenol (2,4-DCP) in an aqueous solution. The effects of several essential operating parameters such as PS dosage and pH on 2,4-DCP degradation were investigated. The removal efficiency of 2,4-DCP (20 mg L-1) was 97.8% in the presence of Fe-EC (50 mg L-1) and PS (1 mmol L-1). Moreover, the average % reaction stoichiometric efficiency (RSE) (calculated for all selected times 5-60 min) was maintained at 23.07%. Electron paramagnetic resonance (EPR), classical radical scavenging experiments, and density functional theory (DFT) calculations were integrated for a mechanistic study, which disclosed that the active species in the system were identified as SO4⦁-, •OH, and O2⦁-. Moreover, the iron-carbon micro-electrolysis/PS (ICE-PS) system had a high tolerance to a wide range of pH, which would provide theoretical guidance for the treatment of organic pollutants in practical industrial wastewater.