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Herein, a highly effective ɑ-MnO2/Fe3O4 nanocomposite was synthesized employing a hydrothermal process and characterized by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, vibrating sample magnetometer (VSM), Fourier transform infrared spectroscopy (FTIR), and UV–visible spectroscopy. The ɑ-MnO2/Fe3O4 photocatalyst flaunts two phases: magnetic magnetite (Fe3O4) nanoparticles of 22±5 nm agglomerated on ɑ-MnO2 1-D nanowire of ∼1.5 µm length and 50±10 nm in diameter. The results exhibited ∼100% photocatalytic degradation of 2,4-DCP under UV-visible irradiation within 80 min at pH 9. The photocatalytic experimental values were fitted linearly with first-order reaction exhibiting k = 0.065 min−1, t1/2 = 10.45 min, and R2 = 0.98 for UV-visible light and k = 0.028 min−1, t1/2 = 34 min and R2 = 0.97 for reaction under sunlight. Additionally, the nanocomposite photocatalyst was easily recoverable using an external magnetic field at room temperature with high stability. Therefore, a simple synthesis method, a synergistic effect between ɑ-MnO2 and Fe3O4, an excellent adsorption-induced photocatalytic activity, easy magnetic recovery, and robustness for reusability make the nanocomposite an outstanding material for environmental sustainability and solar energy harvesting.

Dissolved organic matter (DOM), which is ubiquitously distributed in groundwater, has a crucial role in the fate and reactivity of iron materials. However, there is a lack of direct evidence on how different DOMs interact with nFe/Ni in promoting or inhibiting the dechlorination efficiency of chlorinated aromatic contaminants. By comparing humic acid (HA), fulvic acid (FA), and biochar-derived dissolved organic matter (BDOM) at different pyrolysis temperatures, we first demonstrated that the dechlorination effect of nFe/Ni on 2,4-dichlorophenol (2,4-DCP) depended on the nature of DOMs and their adsorption on nFe/Ni. HA showed an enhancing effect on the dechlorination of 2,4-DCP by nFe/Ni, while the inhibition effect of other DOMs resulted in the following dechlorination order: BDOM300 ≈FA>BDOM700 ≈BDOM500. The C2 component with higher aromaticity and molecular weight promoted the corrosion of nFe/Ni and the production of reactive hydrogen atoms (H*). The effects of different DOMs on nFe/Ni include that (1) HA accelerates the corrosion and H* production of nFe/Ni, (2) FA and BDOM300 enhance the corrosion but inhibit H* production, and (3) Both nFe/Ni corrosion and H* formation are suppressed by BDOM500/BDOM700. Therefore, this study will provide a reference for understanding the nature of DOM-nFe/Ni interaction and improving the catalytic activity of nFe/Ni when different DOMs coexist in practical applications., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this study, the activated carbons (ACs) were prepared from guava seeds via two stages activation. The dried guava seeds were semi-carbonized at 300 °C for 1 h, and then the carbonized samples were impregnated with zinc chloride (ZnCl2). The ZnCl2: sample impregnation ratios (w/w) were altered from 1:1 to 5:1. The ACs were characterized by the yield percentage, ash content, moisture content, pH value, adsorption quality of 2,4-dichlorophenol (2,4-DCP) and surface functional groups. The surface area of the best produced AC3 was found to be 919.40 m2 g−1. It was found that AC3 had highest 2,4-DCP adsorption capacity, which was 20.9 mg g−1. The 2,4-DCP adsorption kinetic of prepared AC3 was pseudo-second order with correlation value of 0.995. In addition, the 2,4-DCP adsorption capacity of AC3 was fitted to the Langmuir model with correlation coefficient value of 0.977, indicating that chemisorption was a major contributor to the adsorption process.

2,4-Dichlorophenol, which is largely employed in herbicides and industrial production, is frequently detected in ecosystems and poses risks to human health and environmental safety. Microbial communities are thought to perform better than individual strains in the complete degradation of organic contaminants. However, the synergistic degradation mechanisms of the microbial consortia involved in 2,4-dichlorophenol degradation are still not widely understood. In this study, a bacterial consortium named DCP-2 that is capable of degrading 2,4-dichlorophenol was obtained. Metagenomic analysis, cultivation-dependent functional verification, and co-occurrence network analysis were combined to reveal the primary 2,4-dichlorophenol degraders and the cooperation patterns in the consortium DCP-2. Metagenomic analysis showed that Pseudomonas, Achromobacter, and Pigmentiphaga were the primary degraders for the complete degradation of 2,4-dichlorophenol. Thirty-nine phylogenetically diverse bacterial genera, such as Brucella, Acinetobacter, Aeromonas, Allochromatium and Bosea, were identified as keystone taxa for 2,4-dichlorophenol degradation by keystone taxa analysis of the co-occurrence networks. In addition, a stable synthetic consortium of isolates from DCP-2 was constructed, consisting of Pseudomonas sp. DD-13 and Brucella sp. FZ-1; this synthetic consortium showed superior degradation capability for 2,4-dichlorophenol in both mineral salt medium and wastewater compared with monoculture. The findings provide valuable insights into the practical bioremediation of 2,4-dichlorophenol-contaminated sites., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In this study, a dicyandiamide residue-derived carbon material (DWC-800) was fabricated through a two-step process involving ball-milling nitrogen (N) doping and high-temperature annealing, and then utilized for peroxodisulfate (PDS) activation in the removal of 2,4-dichlorophenol (2,4-DCP). The obtained DWC-800, with very low N content (0.52 at.%), exhibited highly efficient PDS activation, resulting in complete removal of 2,4-DCP in 60 min. This performance was superior to that of the material with high N content (15.4 at.%), which was prepared using only one-step ball-milling N doping. The N-doped process increased the defective degree of carbocatalyst, and these reactive carbon defects rather than N species greatly improved the adsorption and catalytic activity. The results of quenching experiments and electron paramagnetic resonance demonstrated that PDS activation by DWC-800 for 2,4-DCP degradation followed a nonradical pathway, leading to the production of both singlet oxygen ( 1 O 2 ) and carbon-PDS* complex. Notably, electron transfer mediated by the carbon-PDS* complex played a significant role in the degradation of 2,4-DCP. Overall, this study gets new insights into the role of N doping in mediating the structural properties of the carbocatalyst and its catalytic performance, and provides a theoretical basis for the utilization of dicyandiamide waste residue for wastewater remediation., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In this study, modification of commercial activated carbon (AC) has been examined for the removal of 2,4-dichlorophenol (2,4-DCP) from aqueous solutions. The modified process involves impregnation of phosphoric acid at ratios of 0.6–2.4 followed by 500 °C and 700 °C for 2 h. The effect of different impregnation ratios and activation temperatures was studied. Physical and chemical characterization of modified AC was conducted including percentage yield, moisture content, ash content, pH, morphology study and functional groups. The adsorption of 2,4-DCP by modified AC was also investigated. Various tests were conducted on the unmodified AC and chemically modified AC at different contact times (5–60 min) and adsorbent dosages (0.1–0.9 g). Results revealed that the modified AC (AC2) prepared with impregnation ratio, Xp value of 1.2 at 500 °C for 2 h was found to have the highest percentage removal of 2,4-DCP (50 ppm), which is 93.63%. The modified AC showed better capability to adsorb 2,4-DCP from aqueous solutions, the percentage removal was improved to 20.40%. Elovich and intraparticle diffusion kinetic models were used to test the adsorption kinetics. The adsorption of 2,4-DCP proved to fit better in the intraparticle diffusion model compared to Elovich equation. The mechanism of the adsorption process was determined by the intraparticle model.

The dehaloperoxidase-hemoglobin (DHP), first isolated from the coelom of a marine terebellid polychaete, Amphitrite ornata, is an example of a multi-functional heme enzyme. Long known for its reversible oxygen (O 2 ) binding, further studies have established DHP activity as a peroxidase, oxidase, oxygenase, and peroxygenase. The specific reactivity depends on substrate binding at various internal and external binding sites. This study focuses on comparison of the binding and reactivity of the substrate 2,4-dichlorophenol (DCP) in the isoforms DHPA and B. There is strong interest in the degradation of DCP because of its wide use in the chemical industry, presence in waste streams, and particular reactivity to form dioxins, some of the most toxic compounds known. The catalytic efficiency is 3.5 times higher for DCP oxidation in DHPB than DHPA by a peroxidase mechanism. However, DHPA and B both show self-inhibition even at modest concentrations of DCP. This phenomenon is analogous to the self-inhibition of 2,4,6-trichlorophenol (TCP) at higher concentration. The activation energies of the electron transfer steps in DCP in DHPA and DHPB are 19.3 ± 2.5 and 24.3 ± 3.2 kJ/mol, respectively, compared to 37.2 ± 6.5 kJ/mol in horseradish peroxidase (HRP), which may be a result of the more facile electron transfer of an internally bound substrate in DHPA. The x-ray crystal structure of DHPA bound with DCP determined at 1.48 Å resolution, shows tight substrate binding inside the heme pocket of DHPA (PDB 8EJN). This research contributes to the studies of DHP as a naturally occurring bioremediation enzyme capable of oxidizing a wide range of environmental pollutants., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

The integration of iron-based materials and anaerobic microbial consortia has been extensively studied owing to its potential to enhance pollutant degradation. However, few studies have compared how different iron materials enhance the dechlorination of chlorophenols in coupled microbial systems. This study systematically compared the combined performances of microbial community (MC) and iron materials (Fe 0 /FeS 2 +MC, S-nZVI+MC, n-ZVI+MC, and nFe/Ni+MC) for the dechlorination of 2,4-dichlorophenol (DCP) as one representative of chlorophenols. DCP dechlorination rate was significantly higher in Fe 0 /FeS 2 +MC and S-nZVI+MC (1.92 and 1.67 times, with no significant difference between two groups) than in nZVI+MC and nFe/Ni+MC (1.29 and 1.25 times, with no significant difference between two groups). Fe 0 /FeS 2 had better performance for the reductive dechlorination process as compared with other three iron-based materials via the consumption of any trace amount of oxygen in anoxic condition and accelerated electron transfer. On the other hand, nFe/Ni could induce different dechlorinating bacteria as compared to other iron materials. The enhanced microbial dechlorination was mainly due to some putative dechlorinating bacteria (Pseudomonas, Azotobacter, Propionibacterium), and due to improved electron transfer of sulfidated iron particles. Therefore, Fe 0 /FeS 2 as a biocompatible as well as low-cost sulfidated material can be a good alternative for possible engineering applications in groundwater remediation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Rapid quantification of environmental pollutants is important for water quality control and environmental monitoring. In this work, we report the development of molecularly imprinted polymers (MIPs) obtained from poly(methyl vinyl ether-alt-maleic acid) polymer. The synthesized materials were used for selective preconcentration of 2,4-dichlorophenol, a priority pollutant which creates a threat to public health. The structure of poly(methyl vinyl ether-alt-maleic acid) was functionalized with 4-aminomethylpyridine (4-AMP) to incorporate pyridine groups presumably responsible for increased affinity towards 2,4-dichlorophenol. The synthesis was performed with different degree (10%, 20% and 30%) of 4-AMP functionalization to investigate the influence of pyridine group content on the final MIPs properties. The molecular imprinting process was conducted by amidation of polymers' anhydride groups with diethylenetriamine. Moreover, the experimental data indicated that maximum adsorption capacity was observed for the highest 4-AMP functionalization degree. Similarly, MIPs with the highest 4-AMP content proved to possess the highest selectivity towards the analyte. Finally, the functionalized MIPs were used to quantify 2,4-dichlorophenol by their direct introduction into a specially designed ambient mass spectrometry setup. The detection limits were improved significantly over the ones measured for pure analyte solution. The proposed analytical technique was used to quantify 2,4-dichlorophenol in river water and wastewater samples. Good recovery results were obtained, which proves that the method can be used for analysis of complex real-life samples., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Michal Ceglowski reports financial support was provided by National Science Centre Poland., (Copyright © 2023 Elsevier B.V. All rights reserved.)

An effective as well as eco-friendly photodegradation methods by atoxic and easily reusable photocatalysts are essential for wastewater treatment. Silver phosphate (Ag 3 PO 4 ) specifically in tetrahedral shape is one of the superior catalysts under visible light but its photocorrosion, poor electron transfer ability and low surface adsorption properties limits its applications. Combination of Ag 3 PO 4 and nitrogen doped reduced graphene oxide (NrGO) having higher in surface area, ample functional groups and hetero atom doping is expected to get over the problem. Further addition of a spinel ferrite (CuFe 2 O 4 ) could enhance the visible light response activity and helps in easy separation of catalyst for reuse. Given the merits of Ag 3 PO 4 , NrGO and CuFe 2 O 4 we rationally integrated a novel magnetically separable stable Ag 3 PO 4 /NrGO/CuFe 2 O 4 photocatalyst for efficient detoxification of 2,4-dichlorophenol (2,4-DCP). About 95.3% degradation efficiency was achieved by Ag 3 PO 4 /NrGO/CuFe 2 O 4 (k = 0.01978 min -1 ) which was ~2.6 times higher than pure Ag 3 PO 4 (k = 0.00747 min -1 ) in 60 min of visible light irradiation. The Ag 3 PO 4 /NrGO/CuFe 2 O 4 heterojunction was able to separate and recycle easily using an external magnetic field due to its strong magnetism, and after 5 recycles it showed 88.6% of degradation efficiency revealed its higher stability and recyclability. The photocatalytic mechanism of Ag 3 PO 4 /NrGO/CuFe 2 O 4 was explained by heterojunction energy-band theory. In addition, the plausible intermediate products of 2,4-dichlorophenol were analyzed by ESI/LC-MS and proposed the pathway. Moreover, the phytotoxicity was also studied on V. radiata in which GI (germination index) was found to be 11.97% before degradation, while 80.31% of GI was observed in 60 min of degradation which revealed that more significant reduction in toxicity was attained on this photodegradation., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Transformation of chloro-organic compounds by nFe(0) has been studied extensively, but limited study exists on the transformation and fate of nFe(0) during the dechlorination of chloro-organics even though such knowledge is important in predicting its surface chemistry, particularly, toxicity in the environment. In this study, the nFe(0) core became hollowed, collapsed and gradually corroded into poorly crystallized ferrihydrite (Fe 5 O 3 (OH) 9 ) at the pristine reaction time, which later gave rise to lath-like lepidocrocite (γ-FeOOH), acicular goethite (α-FeOOH) and cubic magnetite (Fe 3 O 4 ) by the end of the reaction time (120 min). Also, dechlorination of 2,4-DCP into 2-CP, 4-CP and phenol was achieved within 120 min. The rapid dechlorination of 2,4-DCP and transformation of nFe(0) could not be achieved significantly without doping Ni on nFe(0) and supporting on attapulgite. The schematic representation of the transformation and compositional evolution of nFe(0) in A-nFe/Ni was proposed. These findings are critical in understanding the compositional evolution and the fate of nFe(0) upon reaction with chloro-organics and can provide guidance for more efficient uses of the nFe(0) reactivity towards the target contaminants in groundwater remediation., (Copyright © 2021 Elsevier B.V. All rights reserved.)

We reported one novel strategy via band engineering of the semiconductor support to optimize the metal-support interactions at a Mott-Schottky heterojunction interface and enhance the metal's electrocatalytic hydrodechlorination (EHDC) performance. Taking palladium-polymer carbon nitride (Pd/PCN) as a model, the band tuning of PCN by heteroatomic phosphorus (P) doping substantially boosted the EHDC of 2,4-dichlorophenol (2,4-DCP, one typical chlorinated organic pollutants (COPs)) on Pd, and a peak specific activity of 0.172 min -1 cm Pd -2 was achieved by Pd/P-PCN-0.25 (0.25 reflected the P content, and denoted the mass ratio of the P source to PCN precursor used in P-PCN synthesis), quadrupling 0.041 min -1 cm Pd -2 of Pd/C and outperforming most of the reported catalysts. The mechanism study revealed the P doping in PCN enabled the positive shift of its Fermi level, which weakened the Pd-PCN interactions and alleviated the electron excess of Pd in Pd/PCN. The P-PCN in Pd/P-PCN-0.25 with the ideal band structure evoked a Pd electronic state that maximized EHDC efficiency. Further investigation into the intermediate products of EHDC on Pd/P-PCN and the biological safety of the 2,4-DCP-contaminated water after EHDC treatment demonstrated the EHDC over our catalyst was environmental-benignity for COPs abatement., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In recent times, cost effective synthesis of semiconductor materials has been a subject of concern for the day to today applications. In this work, novelty has been made on the facile synthesis of metal oxides (TiO 2 and CeO 2 ) and nanocomposites (TiO 2 -CeO 2 ) through sol-gel and precipitation methods of imparting lemon extract. The synthesized materials behave as the functional catalysts which has been further carried out for the photocatalytic degradation against 2,4-Dichlorophenol (2,4-DCP). The materials are then valued for the structural and optical properties. The lemon extract used in synthesis has played a premier role in upgrading the charge carrier separation, bandgap, and size reduction of the composite system. Further, the CeO 2 supported TiO 2 sample acts as the better visible light catalyst, due to the prevention of aggregation and existence of line dislocation that supported to access the additional electron trap sites., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The contribution of Cu(III) produced during heterogeneous peroxydisulfate (PDS) activation to pollutant removal is largely unknown. Herein, a composite catalyst is prepared with Cu-based metal organic framework (Cu-MOF) derived Cu nanoparticles decorated in a three-dimensional reduced graphene oxide (3D RGO) network. The 3D RGO network overcomes the aggregation of nanosized zero-valent copper and reduces the copper consumption during the PDS activation reaction. The Cu/RGO catalyst exhibits high catalytic activity for 2,4-dichlorophenol (2,4-DCP) degradation in a wide pH range of 3-9, with a low Cu dosage that is only 0.075 times that of previous reports with zero-valent copper. Moreover, a high mineralization ratio (69.2 %) of 2,4-DCP is achieved within 30 min, and the Cu/RGO catalyst shows high reactivity toward aromatic compounds with hydroxyl and chlorinated groups. Unlike normal sulfate radical-based advanced oxidation, alcohols show negligible impacts on the reaction, suggesting that Cu(III), rather than SO 4 - and OH, dominates the degradation process. We believe that PDS activation by 3D Cu/RGO, with Cu(III) as the main active species, provides new insights in selective organic pollutant removal in wastewater treatment., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The sulfate radical based advanced oxidation processes (SR-AOPs) has shown great potential in environmental remediation. In recent years, metal-free catalysts have attracted great attention due to their properties of low environmental risk and high catalytic activity. Among them, biochar-based catalysts are widely studied for their low cost by using substance existing in nature as raw material. In this work, egg shell derived biochar (ES-biochar), which was prepared by a simple one-pot pyrolysis method, has been proven to be an effective and innovative catalyst to activate persulfate for aqueous organic pollutant degradation. In addition, ES-biochar showed superior performance in the degradation reaction with removal efficiency of more than 90% in 120 min for 2,4-dichlorophenol (2,4-DCP), which was selected as a representative organic pollutant. Further quenching tests and electron spin resonance spectroscopy demonstrated that both free-radicals and non-radicals pathways were involved in this process, and OH dominated in free-radicals process. More importantly, this work not only proposed a novel biochar material as an efficient persulfate activator, but also provided a value-added reuse approach for egg shell in line with the concept of resource recycling and environmental sustainability., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this work, a Z-scheme BiFeO 3 -g-C 3 N 4 -WO 3 (BFO-CN-WO) photocatalyst has been synthesized via a wet chemical method and utilized in photocatalysis for hydrogen generation and 2,4-dichlorophenol (2,4-DCP) degradation under visible light irradiation. The resultant photocatalyst showed 90 μmol·h -1  g -1 H 2 evolution activity and 63% 2,4-DCP degradation performance, which is 12 and 4.2 times higher than the pristine g-C 3 N 4 respectively. The fascinating photocatalytic performance is attributed to the strong interfacial contact between g-C 3 N 4 and the coupled BiFeO 3 and WO 3 component, which greatly improved the visible light absorption and charge carriers' separation. The designed Z-scheme heterojunction is a successful strategy for enhancing the separation efficiency of photo-induced charge carriers at the interface while retaining outstanding redox ability. During 2,4-DCP degradation, LC/MS technique was used to detect the reaction intermediates. According to the LC/MS results, several new intermediates such as 2,3-dichloro-6-(2,4-dichlorophenoxy)phenol (m/z = 306), 2,4-dichlorophenyl hydrogen carbonate (m/z = 207), 2,4-dichlorobenzen-1,3-diol (m/z = 177) and phenyl hydrogen carbonate (m/z = 137) were detected. Based on these intermediates, 2,4-DCP degradation pathway is proposed. The fluorescence (FL) and electron paramagnetic resonance (EPR) results reveal that the •OH plays an important role in the 2,4-DCP degradation. The fabricated photocatalyst can be utilized in the field of photocatalysis for practical applications., Competing Interests: Declaration of Competing Interest None., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Surface runoff is one of the major pollution sources impacting the quality of the surrounding waterbody. In this study, a highly-bioreactive top-layer soil incorporated with microorganism (BO) and peanut shell (PS) biochar or dairy manure (DM) biochar was proposed for removal of 2,4-dichlorophenol (2,4-DCP) from contaminated surface runoff. Both batch test and sandbox experiment consistently revealed that PS coupled with BO amendment (PS + BO) was most effective for sorption and degradation of 2,4-DCP, compared to BO and DM alone or in combination. About 77% of 6000 μg∙L -1 2,4-DCP was absorbed within 36 h in the original low permeability bioreactive PS + BO soil layer (15 cm long×15 cm wide×4.5 cm deep) with the 0.33 L∙day -1 processing capacity of surface runoff. Increasing the addition of quartz sand into the bioreactor soil layer by threefold the original bioreactor improved the processing capacity to 17.5 L∙day -1 . However, this permeability-optimized bioreactive layer was still not large enough to remove 2,4-DCP completely. The optimized scale by the multi-process coupling model of the convection, dispersion, adsorption, and degradation was 60 cm long × 60 cm wide × 18 cm deep where the processing capacity of 280 L·day -1 reached and 97.3% of 2,4-DCP was removed, correspondingly the 2,4-DCP concentration could meet the standard limit. In addition, the obtained model parameters showed that the biochar or microorganism significantly decreased the dispersion coefficient D of 2,4-DCP in the bioreactive layer. The 2,4-DCP distribution coefficient K d , and first-order reaction rate λ in the PS+BO system significantly greater than that in the control, BO, and PS systems. Results from this study indicated that the top-layer soil incorporated with microorganisms and biochar is a feasible and effective approach for the surface runoff treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Inorganic and organic pollutants present a hazard to surface and groundwater resources. Peroxymonosulfate (PMS, HSO 5 - on the PMS oxidation of organic compounds. In this study, 2,4-dichlorophenol (2,4-DCP) was used as a model pollutant. At a PMS concentration of 2.0 mM, Cl - on the PMS oxidation of organic compounds. In this study, 2,4-dichlorophenol (2,4-DCP) was used as a model pollutant. At a PMS concentration of 2.0 mM, Cl - concentration of 50 mM, and solution pH of 7.0, 2,4-DCP was completely degraded by PMS in the presence of Cl - (PMS/Cl - system), while PMS alone exhibited almost no reactivity with 2,4-DCP. The degradation of 2,4-DCP was optimized at a solution pH of 8.4 and high concentrations of PMS and Cl - . Quenching experiments and degradation pathway analyses indicated that HClO was responsible for 2,4-DCP oxidation, and HClO was mainly generated by the interaction of Cl - with HSO 5 - , rather than SO 5 2- . Consequently, the transformation from HSO 5 - to HClO appeared under a solution pH of 10.0 and was favored in an acidic solution. Given the ambient pH and Cl - concentrations of saline waters, a considerable amount of HClO may be produced by the interaction of PMS with Cl - in the oxidant delivery stage of ISCO processes. Interestingly, H 2 O 2 and peroxydisulfate did not exhibit reactions similar to those of PMS. This research indicated that caution must be exercised when choosing an oxidant for ISCO processes in saline waters., Competing Interests: Declaration of competing interest We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled, “Oxidation of 2,4-Dichlorophenol in Saline Water by Unactivated Peroxymonosulfate: Mechanism, Kinetics and Implication for in-situ Chemical Oxidation”., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The biocomposites of polypyrrole (PPY), polyaniline (PANI) and sodium alginate (NaAlg) with cellulosic biomass barley husk (BH) were prepared and employed for the removal of 2,4-dichlorophenol (2,4-DCP) form aqueous media. The sorption of 2,4-DCP was studied using native and biocomposites (PPY/BH, PANI/BH and NaAlg/BH) as function of various process variables. The maximum sorption (q e , 7.55-24.57 mg/g) of 2,4-DCP was achieved in the range of 7-10 pH, 0.05 g composite dose, 25 mg/L initial concentration of 2,4-DCP and 120 min contact time at 30 °C. The FTIR analysis revealed the involvement of amino, hydroxyl and carboxylic groups for the binding of 2,4-DCP on the surface of biocomposites. The Freundlich and pseudo second order kinetics models best explained the 2,4-DCP adsorption on to the biocomposites. The ∆G, ∆H and ∆S parameters were also computed, which revealed the favorable and exothermic adsorption nature of 2,4-DCP. Presence of salts affected the 2,4-DCP adsorption negatively. HCl found to be efficient desorbing agent for 2,4-DCP from composites and up to 65.12% was eluted using 0.5 N solution. In view of promising efficiency, the biocomposites have potential to remove 2,4-DCP form industrial effluents., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The rise in manufacture and use of carbon nanotubes has aroused the concern about their potential risks associated with coexisting pollutants in the aquatic environment. 2,4-dichlorophenol (2,4-DCP), with a high toxicity to many aquatic organisms, is a widespread pollutant resulting from the extensive use of pesticides and preservatives. In this article, the adsorption of 2,4-DCP by riverine sediment and the responses of sediment microbial community to 2,4-DCP were studied in the presence of multi-walled carbon nanotubes (MWCNTs). Adding MWCNTs significantly increased the adsorption amount of sediment for 2,4-DCP from 0.541 to 1.44 mg/g as the MWCNT concentration increased from 0 to 15 mg/g. The responses of sediment microbial community were determined after one-month exposure to MWCNTs at different concentrations (0.05, 0.5, 5, and 50 mg/g). The microbial biomass carbon in the sediment contaminated with 2,4-DCP increased in the presence of 5 mg/g of MWCNTs (from 0.06 to 0.11 mg/g), but not significantly changed at other MWCNT concentrations. For the sediments contaminated with 2,4-DCP, the presence of MWCNTs made no difference to urease activity, while the dehydrogenase activity slightly increased with the addition of 5 mg/g of MWCNTs and decreased in the presence of 50 mg/g of MWCNTs. The changes of sediment bacterial communities were further determined by 16S rRNA gene sequencing. Based on the weighted UniFrac distance between communities, the clustering analysis suggested that the contamination of 2,4-DCP affected the bacterial community structure in a greater degree than that caused by MWCNTs at relatively low concentrations (≤5 mg/g). Bacteroidetes, Planctomycetes, and Nitrospirae were feature bacterial phyla to reflect the effects of MWCNTs and 2,4-DCP on sediment bacterial community. These results may contribute to the understanding of microbial community response to co-exposure of MWCNTs and 2,4-DCP and the assessment of associated ecological risks., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A 61.3 kDa Phenol hydroxylase (PheA) was purified and characterized from Pseudomonas sp. KZNSA (PKZNSA). Cell free extract of the isolate grown in mineral salt medium supplemented with 600 ppm phenol showed 21.58 U/mL of PheA activity with a specific activity of 7.67 U/mg of protein. The enzyme was purified to 1.6-fold with a total yield of 33.6%. The purified PheA was optimally active at pH 8 and temperature 30 °C, with ≈95% stability at pH 7.5 and temperature 30 °C after 2 h. The Lineweaver-Burk plot showed the v max and K m values of 4.04 µM/min and 4.03 µM, respectively, for the substrate phenol. The ES-MS data generated from the tryptic digested fragments of pure protein and PCR amplification of a ≈600 bp gene from genomic DNA of PKZNSA lead to the determination of complete amino acid and nucleotide sequence of PheA. Bioinformatics tools and homology modelling studies indicated that PheA from PKZNSA is likely a probable protein kinase UbiB (2-octaprenylphenol hydroxylase) involving Lys and Asp at positions 153 and 288 for binding and active site, respectively. Characterization and optimization of PheA activity may be useful for a better understanding of 2,4-dichlorophenol degradation by this organism and for potential industrial application of the enzyme., Competing Interests: Declaration of Competing Interest All the authors declare no conflicts of interest., (Copyright © 2019 Elsevier B.V. All rights reserved.)

2,4-Dichlorophenol (2,4-DCP) is ubiquitous in aquatic environment and has potential estrogenic effect on fish. However, the effect of 2,4-DCP on sex differentiation of zebrafish (Danio rerio) and the underlying mechanism are largely unknown. To address these questions, zebrafish larvae at 20 or 30 days post fertilization (dpf) were exposed to 2,4-DCP (0, 80 and 160 μg L -1 ) with/without 5-aza-2'-deoxycytidine (5AZA, 50 μg L -1 ) for 10 days. The sex ratios and the expressions of male-related genes including amh, gata4, nr5a1a, nr5a2 and sox9a were analyzed. In addition, the DNA methylation levels of amh, nr5a2 and sox9a were examined. The results showed that 2,4-DCP exposure resulted in significant increase of female ratios both in 20-30 and 30-40 dpf groups. Correspondingly, the expressions of gata4, nr5a1a, nr5a2 and sox9a were decreased by 2,4-DCP exposure in two treatment periods. However, the transcript of amh was decreased by 2,4-DCP exposure only from 30 to 40 dpf. The DNA methylation levels of amh, nr5a2 and sox9a were increased following 2,4-DCP exposure. Moreover, the addition of 5AZA could counteract the effects including feminization, disturbance of gene expression and DNA hypermethylation caused by 2,4-DCP. These results indicated that the feminizing effect of 2,4-DCP was accomplished by regulating the expression of male-related genes through DNA methylation., (Copyright © 2019 Elsevier Inc. All rights reserved.)

We have rationally designed and fabricated of "face-to-face" 3D/2D In 2 O 3 nanocube/ZnIn 2 S 4 nanosheet heterojunction by growing ZnIn 2 S 4 nanosheets on the surfaces of In 2 O 3 cubes as photocatalysts for 2,4-dichlorophenol (2,4-DCP) degradation under visible light. Herein, the unique 3D/2D In 2 O 3 nanocube/ZnIn 2 S 4 nanosheet hierarchical structure not only exposes far more abundant heterojunction interface active sites compared to 3D/0D In 2 O 3 nanocube/ZnIn 2 S 4 nanoparticle, but also produces numbers of compact high-speed nanochannels in the junctions, which significantly promotes the separation and migration of photogenerated carriers. Profiting by structural and compositional advantages, the optimized 3D/2D ZnIn 2 S 4 -In 2 O 3 photocatalyst shows excellent photocatalytic activity and stability in the degradation of 2,4-DCP, which is 1.85, 2.60, 3.02 and 3.54-fold higher than that of 3D/0D ZnIn 2 S 4 -In 2 O 3 , ZnIn 2 S 4 nanosheet, ZnIn 2 S 4 nanoparticle and In 2 O 3 , respectively. Meanwhile, the main active species (·O 2 - , ·OH and h + ) produced in the photodegradation process were determined and the intermediates and degradation mechanism were studied in detail. Besides, the application on the removal of 2,4-DCP in natural water and actual wastewaters by 3D/2D ZnIn 2 S 4 -In 2 O 3 also have been studied. This work provides a new strategy for efficiently optimize the advantages of binary nano-architectures to effectively degrade phenolic pollutants in the environment., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Three possible dechlorination mechanisms of chloroorganics by nanoscale zero-valent iron (n-ZVI) have been proposed and widely accepted, however, the main mechanism is still controversial and not verified by experimental results. In this study, 2,4-dichlorophenol (2,4-DCP) was selected as the target pollutant and the experiments were carried out for the screening of the main mechanism of 2,4-DCP dechlorination by n-ZVI and Fe/Ni nanoparticles (n-Fe/Ni). The results indicated that >95% of 2,4-DCP could be dechlorinated to phenol by n-Fe/Ni within 120 min, while 2,4-DCP could hardly be dechlorinated by n-ZVI particles. The active hydrogen atom (H*) that transformed from H 2 under the catalysis of Ni was responsible for >90% of 2,4-DCP dechlorination by n-Fe/Ni and <10% of the dechlorination was attributed to the direct electron transfer from ZVI. Fe 2+ was not able to dechlorinate 2,4-DCP. Correspondently, Ni in n-Fe/Ni mainly acted as a catalyst, while the acceleration of electron transfer from ZVI by Ni had a positive effect on 2,4-DCP dechlorination. The investigations on the relative importance of these three mechanisms are essential to iron-based remediation technology., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Low efficiency is often a problem in electrochemical reductive hydrodechlorination (ERHD) to remove chlorinated compounds such as 2,4-dichlorophenol (24DCP) from water. In this study, a composite molecularly imprinted membrane (MIM)/bipolar membrane (BPM) was introduced onto a palladium-coated titanium mesh electrode (BPM/MIM@Pd/Ti) to increase the concentration of 24DCP on the surface of electrode and ERHD efficiency. The efficiency of ERHD of 24DCP increased from 70 to 88% by introduction of the two membranes, from 71 to 89% by increasing current density from 5.0 to 30 mA/cm 2 , and from 80 to 94% by increasing the electrolyte concentration from 0.25 to 1.00 mol/L. Treatment with Fenton's reagent after ERHD achieved 100% 24DCP removal, with chemical oxygen demand and total organic carbon reductions of 91 and 87%, respectively. Notably, these reductions were greater than obtained from the direct oxidation of the 24DCP solution by Fenton's reagent alone (i.e., 98, 84, and 72%, respectively). No products were detected in solution by GC-MS after treatment with the proposed combination technology. The mechanism of 24DCP removal and degradation involved adsorption, electrochemical hydrodechlorination via H ads , and Fenton oxidation. Results show the process has high potential for removing 24DCP from aqueous solution., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this study, organic-inorganic nanocomposite including mesoporous silica SBA-15 and chitosan was combined using carboxyl-functionalized ionic liquid as the bridging agent (SBA-CIL-CS), and which was characterized by scanning electron microscope, Fourier transform infrared spectroscopy, thermogravimetric analysis, and nitrogen adsorption-desorption isotherms. Thus prepared nanocomposite was applied to laccase immobilization via physical adsorption (SBA-CIL-CS-Lac) and utilized in 2,4-dichlorophenol (2,4-DCP) removal for the first time. SBA-CIL-CS-Lac showed relatively high immobilization efficiency, activity retention (75.3%), pH stability and storage stability. Kinetic experiment showed SBA-CIL-CS-Lac had the eminent affinity to the substrate. Circular dichroism and fluorescence analysis verified the active conformation of SBA-CIL-CS-Lac was maintained well to keep its enzymatic activity. Compared with the previous methods, SBA-CIL-CS-Lac exhibited prominent catalytic efficiency and reusability as well as pH and temperature stability for 2,4-DCP removal. The removal rate of SBA-CIL-CS-Lac for 2,4-DCP could be up to ˜90% after 35 h. Moreover, 58.8% removal rate could be retained after five operation runs. These results indicated that organic-inorganic nanocomposite SBA-CIL-CS was an ideal support for enzyme immobilization., (Copyright © 2019 Elsevier B.V. All rights reserved.)

As a persistent organic pollutant listed in the Stockholm Convention, perfluorooctane sulfonate (PFOS) is extremely refractory to degradation under ambient conditions. Its potential ecotoxicity has aroused great concerns and research interests. However, little is known about the toxicity of PFOS on fungus. In this study, the white rot fungus Phanerochaete chrysosporium (P. chrysosporium) was adopted to assess the toxicity of PFOS in liquid culture. The addition of 100 mg/L PFOS potassium salt significantly decreased the fungal biomass by up to 76.4% comparing with un-amended control during the incubation period. The hyphostroma of P. chrysosporium was wizened and its cell membrane was thickened, while its vesicle structure was increased, based on the observation with scanning electron microscope (SEM) and transmission electron microscope (TEM). Nevertheless, the PFOS dosage of below 100 mg/L did not show a considerable damage to the growth of P. chrysosporium. The degradation of malachite green (MG) and 2,4-dichlorophenol (2,4-DCP) by P. chrysosporium was negatively affected by PFOS. At the initial dosage of 100 mg/L PFOS, the decolorization efficiency of MG and the degradation efficiency of 2,4-DCP decreased by 37% and 20%, respectively. This might be attributed to the inhibition of PFOS on MnP and LiP activities. The activities of MnP and LiP decreased by 20.6% and 43.4%, respectively. At a high dosage PFOS (100 mg/L), P. chrysosporium could show a high adsorption of MG but lose its pollutant degradation ability. Transcriptome analysis indicated that PFOS contamination could lead to the change of gene expression in the studied white rot fungus, and the genes regulating membrane structure, cell redox process, and cell transport, synthesis and metabolism were impacted. Membrane damage and oxidative damage were the two main mechanisms of PFOS' toxicity to P. chrysosporium., (Copyright © 2019 Elsevier Inc. All rights reserved.)

A novel core-shell structured Fe 3 O 4 @GO@MIL-100(Fe) magnetic catalyst was successfully synthesized and used as heterogeneous photo-Fenton catalyst for 2,4-dichlorophenl (2,4-DCP) degradation. The catalyst was fully characterized by X-ray diffraction pattern (XRD), Raman spectroscopy, Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Brunner-Emmet-Teller (BET) and magnetic hysteresis loops measurements. The effects of initial pH, H 2 O 2 concentration, catalyst load and irradiation intensity on 2,4-DCP degradation were also investigated. The results showed that Fe 3 O 4 @GO@MIL-100(Fe) exhibited excellent photo-Fenton catalytic activity, achieving almost 100% of 2,4-DCP degradation within 40 min at reaction condition of 3 mmol/L H 2 O 2 , 50 mg/L 2,4-DCP, pH 5.5 and irradiation intensity of 500 W. The high catalytic activity of Fe 3 O 4 @GO@MIL-100(Fe) can be attributed to the efficient transfer of photo-generated electrons between MIL-100(Fe) and Fe 3 O 4 by GO. The recycling experiments displayed that Fe 3 O 4 @GO@MIL-100(Fe) catalyst possessed good stability and could be easily recovered under an applied magnetic field. Finally, the possible mechanism of 2,4-DCP degradation in the photo-Fenton system catalyzed by Fe 3 O 4 @GO@MIL-100(Fe) was also proposed according to the analyses of reactive species, photoluminescence (PL) emission spectra and the photocurrent responses., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this work, a sensitive and selective electrochemical sensor based on polydopamine-reduced graphene oxide (PDA-rGO) and molecular imprinted polymers (MIP) modified glassy carbon electrode for detection of 2,4-DCP was fabricated. The PDA-rGO was obtained through the auto polymerization of dopamine in graphene oxide solution at an alkaline environment. The MIP film was performed on the surface of the PDA-rGO modified electrode by electropolymerization the monomer of o-phenylenediamine (o-PD) with the template of 2,4-dichlorophenol (2,4-DCP). The bare hydroxyl and benzene rings of PDA-rGO could attract positive charged o-PD and provide π-π stacking effect with o-PD and 2,4-dichlorophenol, which made the compact imprinted film and more imprinted sites. The Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to character the MIP and NIP modified electrode in the presence of [Fe(CN) 6 ] 3- /[Fe(CN) 6 ] 4- as a probe for signal transduction. The relative current intensity of ferro/ferricyanide decreased linearly with increasing concentration of 2,4-DCP with a detection limit of 0.8 nM (S/N = 3). The MIP sensor had a much higher affinity towards 2,4-DCP than other analogues. The proposed method was successfully applied for the determination of 2,4-DCP in real water samples., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This study aims at investigating the efficiency and kinetics of 2,4-DCP degradation via advanced reduction processes (ARP). Using UV light as activation method, the highest degradation efficiency of 2,4-DCP was obtained when using sulphite as a reducing agent. The highest degradation efficiency was observed under alkaline conditions (pH = 10.0), for high sulphite dosage and UV intensity, and low 2,4-DCP concentration. For all process conditions, first-order reaction rate kinetics were applicable. A quadratic polynomial equation fitted by a Box-Behnken Design was used as a statistical model and proved to be precise and reliable in describing the significance of the different process variables. The analysis of variance demonstrated that the experimental results were in good agreement with the predicted model (R 2  = 0.9343), and solution pH, sulphite dose and UV intensity were found to be key process variables in the sulphite/UV ARP. Consequently, the present study provides a promising approach for the efficient degradation of 2,4-DCP with fast degradation kinetics., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This study explored the potential of composites organo-bentonite/alginate beads as adsorbents for the removal of 2,4-dichlorophenol (2,4DCP) from aqueous solution. Bentonite was firstly modified with cationic surfactants octadecyltrimethylammonium, hexadecyl trimethylammonium and phenyltrimethylammonium, then encapsulated with calcium alginate to form adsorbent composite beads. X-ray diffraction was used to study the change in the structural properties of the samples. The intercalated cationic surfactants were characterized by Fourier transform infrared spectroscopy (FTIR). The adsorption was studied using various operating parameters such as contact time, temperature, pH and initial 2,4DCP concentration. The results showed that the amount of 2,4DCP increased with increasing initial concentration, contact time and temperature indicating that the adsorption process of 2,4DCP onto composites is endothermic. Adsorption of 2,4DCP followed pseudo-second-order kinetics. The Langmuir isotherm model fitted well the isotherm data, indicating a monolayer homogeneous adsorption. The prepared adsorbents exhibited relatively high adsorption capacity of 142 to 391 mg/g founded by this model., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Triclosan is considered as an important contaminant and is widely used in personal care products as an antimicrobial agent. This study demonstrates the biodegradation of triclosan by two freshwater microalgae and the acute toxicity of triclosan and 2,4-dichlorophenol. The effects of culture media and light on biodegradation of triclosan and the changing morphology of microalgae were systematically studied. Geitlerinema sp. and Chlorella sp. degraded 82.10% and 92.83% of 3.99 mg/L of triclosan at 10 days, respectively. The microalgal growth inhibition assay confirmed absence of toxic effects of triclosan on Chlorella sp., even at higher concentration (50 mg/L) after 72 h exposure. HPLC analysis showed that 2,4-dichlorophenol was produced as degradation product of triclosan by Geitlerinema sp. and Chlorella sp. This study proved to be beneficial to understand biodegradation and acute toxicity of triclosan by microalgae in order to provide aquatic environmental protection., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Mechanisms of silver nanoparticles-mediated toxicity to Phanerochaete chrysosporium and the influence of silver nanoparticles (AgNPs) on the biodegradation of 2,4-dichlorophenol (2,4-DCP) have been systematically investigated. AgNPs at low doses (0-60μM) have greatly enhanced the degradation ability of P. chrysosporium to 2,4-DCP with the maximum degradation rates of more than 94%, exhibiting excellent synergies between AgNPs and P. chrysosporium in the degradation of 2,4-DCP. Meanwhile, removal of total Ag was also at high levels and highly pH dependent. However, significant inhibition was highlighted on 2,4-DCP biodegradation and Ag removal upon treatment with AgNPs at high doses and AgNO 3 at low-level exposure. Results also suggested that AgNPs-induced cytotoxicity could arise from the "Trojan-horse" mechanism executing particle effects, ion effects, or both, ruling out extracellularly released Ag + . Moreover, under relatively low concentrations of AgNPs exposure, 2,4-DCP was broken into linear chain organics, and eventually turned into CO 2 and H 2 O through reductive dechlorination and reaction with hydroxyl radicals. FTIR analysis showed that amino, carboxyl, carbonyl, and sulfur-containing functional groups played crucial roles in Ag transportation and the reduction of Ag + to Ag 0 ., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Magnetic multi-walled carbon nanotubes (MWCNTs) were prepared to support Pd/Fe nanoparticles, inhibit the aggregation and passivation, and achieve magnetic separation to avoid the environmental risk of nanoparticles. Rapid adsorption of initial contaminant, steady dechlorination, and gradual desorption of final product was observed. The micromorphology, chemical structure, and components of the nanohybrids were comprehensively characterized by a series of analysis technologies, such as EDX, XRD, SEM, TEM, and XPS. The interactions between the nanohybrids compositions were discussed according to the characterization and experimental data. The whole insight of 2,4-dichlorophenol (2,4-DCP) adsorption- dechlorination-desorption was studied in detail, including the pathways, influence factors, dechlorination kinetics and selectivity. Weak acidity (pH=5.0 and 6.5) favored the 2,4-DCP removal. Satisfactory reactivity of the Pd/Fe-Fe3O4@MWCNTs nanohybrids was observed in five consecutive runs, and 99.2%, 89.6%, 92.1%, 99.8%, and 99.9% of 2,4-DCP was removed, respectively. Most of the final product (phenol) was steadily desorbed to the liquid phase, resulted in the re-exposure of active sites on the nanohybrids and maintained a longer activity., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A series of visible-light responsive photocatalysts prepared using Ag3PO4 immobilized with graphene oxide (GO) with varying GO content were obtained by an electrostatically driven method, and 2,4-dichlorophenol (2,4-DCP) was used to evaluate the performance of the photocatalysts. The composites exhibited superior photocatalytic activity and stability compared with pure Ag3PO4. When the content of GO was 5%, the degradation efficiency of 2,4-DCP could reach 98.95%, and 55.91% of the total organic (TOC) content was removed within 60 min irradiation. Meanwhile, the efficiency of 91.77% was achieved for 2,4-DCP degradation even after four times of recycling in the photocatalysis/Ag3PO4-GO (5%) system. Reactive species of O2(˙-), OH˙ and h(+) were considered as the main participants for oxidizing 2,4-DCP, as confirmed by the free radical capture experiments. And some organic intermediates including 4-chlorophenol (4-CP), hydroquinone (HQ), benzoquinone (BZQ), 2-chlorohydroquinone and hydroxyhydroquinone (HHQ) were detected by comparison with the standard retention times from the high performance liquid chromatography (HPLC). In short, the enhanced photocatalytic property of Ag3PO4-GO was closely related to the strong absorption ability of GO relative to 2,4-DCP, the effective separation of photogenerated electron-hole pairs, and the excellent electron capture capability of GO., (Copyright © 2015. Published by Elsevier B.V.)

For the first time a laccase from Trametes versicolor was immobilized on a natural clinoptilolite with Si/Al=5 to obtain a biocatalyst for environmental applications. Immobilization procedures exploiting adsorption and covalent binding were both tested, and only the last provided enough activity for practical applications. The optimal conditions for the immobilization of the enzyme on the support and the kinetic parameters for the free and covalent bonded laccase were determined. The laccase bonded to the zeolitic support showed a lower activity than the free laccase, but the pH and thermal stability were greater. 20 mg of dry biocatalyst containing 1 U of laccase were able to remove in 50h 73-78% of 2-chlorophenol and 2,4-dichlorophenol in relatively concentrated aqueous solutions (100 μmol L(-1))., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A novel biosorbent, polyvinyl alcohol (PVA)-immobilized Phanerochaete chrysosporium, was applied to the bioremediation of composite-polluted wastewater, containing both cadmium and 2,4-dichlorophenol (2,4-DCP). The optimum removal efficiency achieved was 78% for Cd(II) and 95.4% for 2,4-DCP at initial concentrations of 20 mg/L Cd(II) and 40 mg/L 2,4-DCP. PPBs had significantly enhanced the resistance of P. chrysosporium to 2,4-DCP, leading to the degradation rates of 2,4-DCP beyond 90% with varying initial 2,4-DCP concentrations. This research demonstrated that 2,4-DCP and secreted proteins might be used as carbon and nitrogen sources by PVA-immobilized P. chrysosporium beads (PPBs) for Cd(II) removal. Fourier transform infrared spectroscopy analysis showed that hydroxyl and carboxyl groups on the surface of PPBs were dominant in Cd(II) binding. The mechanism underlying the degradation of 2,4-DCP into fumaric acid and 1-hexanol was investigated. The adsorption-desorption studies indicated that PPBs kept up to 98.9% of desorption efficiency over three cycles., (Copyright © 2015 Elsevier B.V. All rights reserved.)

This paper reports a facile and general method for preparing an imprinted polymer thin shell with Mn-doped ZnS quantum dots (QDs) at the surface of silica nanoparticles by stepwise precipitation polymerization to form the highly-controllable core-shell nanoparticles (MIPs@SiO2-ZnS:Mn QDs) and sensitively recognize the target 2,4-dichlorophenol (2,4-DCP). Acrylamide (AM) and ethyl glycol dimethacrylate (EGDMA) were used as the functional monomer and the cross-linker, respectively. The MIPs@SiO2-ZnS:Mn QDs had a controllable shell thickness and a high density of effective recognition sites, and the thickness of uniform core-shell 2,4-DCP-imprinted nanoparticles was controlled by the total amounts of monomers. The MIPs@SiO2-ZnS:Mn QDs with a shell thickness of 45 nm exhibited the largest quenching efficiency to 2,4-DCP by using the spectrofluorometer. After the experimental conditions were optimized, a linear relationship was obtained covering the linear range of 1.0-84 μmol L(-1) with a correlation coefficient of 0.9981 and the detection limit (3σ/k) was 0.15 μmol L(-1). The feasibility of the developed method was successfully evaluated through the determination of 2,4-DCP in real samples. This study provides a general strategy to fabricate highly-controllable core-shell imprinted polymer-contained QDs with highly selective recognition ability., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Polychlorinated biphenyls (PCBs) and 2,4-dichlorophenol (2,4-DCP) generally led to mixed contamination of soils as a result of commercial and agricultural activities. Their accumulation in the environment poses great risks to human and animal health. Therefore, the effective strategies for disposal of these pollutants are urgently needed. In this study, genetic engineering to enhance PCBs/2,4-DCP phytoremediation is a focus. We cloned the 2,3-dihydroxybiphenyl-1,2-dioxygenase (BphC.B) from a soil metagenomic library, which is the key enzyme of aerobic catabolism of a variety of aromatic compounds, and then it was expressed in alfalfa driven by CaMV 35S promoter using Agrobacterium-mediated transformation. Transgenic line BB11 was selected out through PCR, Western blot analysis and enzyme activity assays. Its disposal and tolerance to both PCBs and 2,4-DCP were examined. The tolerance capability of transgenic line BB11 towards complex contaminants of PCBs/2,4-DCP significantly increased compared with non-transgenic plants. Strong dissipation of PCBs and high removal efficiency of 2,4-DCP were exhibited in a short time. It was confirmed expressing BphC.B would be a feasible strategy to help achieving phytoremediation in mixed contaminated soils with PCBs and 2,4-DCP., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Dispersive liquid-liquid microextraction with solidification of floating organic drop (DLLME-SFO) is one of the most interesting sample preparation techniques developed in recent years. Although several applications have been reported, the potentiality and limitations of this simple and rapid extraction technique have not been made sufficiently explicit. In this work, the extraction efficiency of DLLME-SFO for pollutants from different chemical families was determined. Studied compounds include: 10 polycyclic aromatic hydrocarbons, 5 pesticides (chlorophenoxy herbicides and DDT), 8 phenols and 6 sulfonamides, thus, covering a large range of polarity and hydrophobicity (LogKow 0-7, overall). After optimization of extraction conditions using 1-dodecanol as extractant, the procedure was applied for extraction of each family from 10-mL spiked water samples, only adjusting sample pH as required. Absolute recoveries for pollutants with LogKow 3-7 were >70% and recovery values within this group (18 compounds) were independent of structure or hydrophobicity; the precision of recovery was very acceptable (RSD<12%) and linear behavior was observed in the studied concentration range (r(2)>0.995). Extraction recoveries for pollutants with LogKow 1.46-2.8 were in the range 13-62%, directly depending on individual LogKow values; however, good linearity (r(2)>0.993) and precision (RSD<6.5%) were also demonstrated for these polar solutes, despite recovery level. DLLME-SFO with 1-dodecanol completely failed for extraction of compounds with LogKow≤1 (sulfa drugs), other more polar extraction solvents (ionic liquids) should be explored for highly hydrophilic pollutants., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Human exposure to modern non-persistent chemicals is difficult to ascertain in epidemiological studies as exposure patterns and excretion rates may show temporal and diurnal variations. The aim of this study was to assess the temporal variability in repeated measurements of urinary excretion of bisphenol A (BPA) and seven other phenols. All analytes were determined using TurboFlow-LC-MS/MS. Two spot, three first morning and three 24-h urine samples were collected from 33 young Danish men over a three months period. Temporal variability was estimated by means of intraclass correlation coefficients (ICCs). More than 70% of the urine samples had detectable levels of BPA, triclosan (TCS), benzophenone-3 (BP-3) and sum of 2,4-dichlorophenol and 2,5-dichlorophenol (ΣDCP). We found low to moderate ICCs for BPA (0.10-0.42) and ΣDCP (0.39-0.72), whereas the ICCs for BP-3 (0.69-0.80) and TCS (0.55-0.90) were higher. The ICCs were highest for the two spot urine samples, which were collected approximately 4 days apart, compared with the 24-h urine samples and the first morning urine samples, which were collected approximately 40 days apart. A consequence of the considerable variability in urinary excretion of BPA may be misclassification of individual BPA exposure level in epidemiological studies, which may lead to attenuation of the association between BPA and outcomes. Our data do not support that collection of 24-h samples will improve individual exposure assessment for any of the analysed phenols., (Copyright © 2013 Elsevier Inc. All rights reserved.)