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Magnetic multi-template molecularly imprinted polymers (M-mt-MIPs) were successfully synthesized by surface imprinting and multi-template imprinting strategy, using polydopamine coated magnetic multi-walled carbon nanotubes as supporting materials, five typical chlorophenols (CPs) as templates, methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linker. Compared to non-imprinted polymers (NIPs), the as-prepared M-mt-MIPs showed high adsorption capacity (32.58‒80.63 mg g -1 ), rapid mass transfer and specific selectivity for the five targeted CPs, which were applied as magnetic solid-phase extraction (MSPE) adsorbents. Parameters affecting MSPE efficiency were detailed investigated, such as adsorbents dosage, sample pH, extraction time, type and volume of desorption solvent and salt effect. Combined with HPLC-DAD, a simple, rapid and sensitive method was established, showing good linearity (2‒200 μg L -1 ), low limits of detection (0.32‒0.49 μg L -1 ), and high enrichment factors (35.2‒108). The developed M-mt-MIPs-MSPE-HPLC method was applied to enrich and determine CPs in tannery wastewater, wet-blue and crust leather, and satisfactory spiking recoveries were attained in the range of 73.95‒109.7% with relative standard deviations (RSDs) of 2.13-8.48%. This study provided a new alternative material and method to rapid simultaneously extract and analyze low concentration of typical CPs in complicated matrices., 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 paper, the adsorption of the chlorinated organic compound, 2,4-dichlorophenol, using activated carbon (AC), bagasse fly ash (BFA) and rice husk fly ash (RHFA) in a packed bed column was simulated using Aspen Adsorption software. The purpose of this study was to demonstrate the effectiveness of simulation software for identifying alternative low-cost adsorbents and optimising the adsorption process. The effect of process parameters such as initial concentration, bed height and inlet feed flow rate were evaluated using breakthrough curves. It was shown that the longest breakthrough times were at a higher bed height of 3 m and lower flow rate of 2 m 3 /hr and concentration had no effect on breakthrough time. After optimisation using response surface methodology, the AC, BFA and RHFA had a breakthrough time of 534, 426 and 209 s, respectively. This shows the potential of BFA as a potential alternative for AC for the adsorption of 2,4-dichlorophenol and shows RHFA to be a relatively poor adsorbent in comparison. The economic evaluation illustrates that the overall cost of wastewater treatment with BFA and RHFA is lower than AC. The cost for the BFA and RHFA adsorbents is only a handling charge, but the cost for using AC adsorbent is £10,603/year. Therefore, the company can produce 17,520 m 3 /year of fresh water from the adsorbent and save £87,600/year. Therefore, it was concluded that BFA had a slightly weaker adsorption efficiency than AC but was more cost effective, allowing it to be more affordable and increasing its availability.

Electrocatalysis offers great promise for water purification but is limited by low active area and high uncontrollability of electrocatalysts. To overcome these constraints, we propose hybrid bulk electrodes by synthesizing and binding a Pd nanocatalyst (nano-Pd) to the electrodes via amyloid fibrils (AFs). The AFs template is effective for controlling the nucleation, growth, and assembly of nano-Pd on the electrode. In addition, the three-dimensional hierarchically porous nanostructure of AFs is beneficial for loading high-density nano-Pd with a large active area. The novel hybrid cathodes exhibit superior electroreduction performance for the detoxification of hexavalent chromium (Cr 6+ ), 4-chlorophenol, and trichloroacetic acid in wastewater and drinking water. This study provides a proof-of-concept design of an AFs-templated nano-Pd-based hybrid electrode, which constitutes a paradigm shift in electrocatalytic water purification, and broadens the horizon of its potential engineered applications., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Three carbonyl-functional novel hypercrosslinked polymers (HCP-TPS, HCP-TPA, and HCP-TPP) were successfully fabricated through an one-step Friedel-Crafts acylation reaction by copolymerizing paraphthaloyl chloride with triphenylsilane, triphenylamine, and triphenylphosphine, respectively. The resultant HCPs contained plenty of carbonyl-functional groups. Among the series of such HCPs, HCP-TPS displayed the best adsorption capability to chlorophenols (CPs), and thus it was employed as solid-phase extraction (SPE) adsorbent for enrichment of chlorophenols from water, honey, and white peach beverage prior to determination by high-performance liquid chromatography. Under the optimal conditions, the detection limits of the method (S/N = 3) were 0.15-0.3 ng mL -1 for tap water and leak water, 2.5-6.0 ng g -1 for honey sample and 0.4-0.6 ng mL -1 for white peach beverage sample. The recoveries of CPs in the spiked water, honey samples, and white peach beverage were in the range of 89.0-108.4%, 81.4-118.2%, and 85.0-113.5%, respectively. This work provides a new strategy for constructing functionalized HCPs as efficient SPE adsorbents. In this work, three novel hypercrosslinked polymers (HCPs) were synthesized by the Friedel-Crafts alkylation reaction (paraphthaloyl chloride as the alkylating agent, triphenylsilane, triphenylamine, and triphenylphosphine as the aromatic units). Then, HCP-TPS was applied to soild-phase extraction sorbent for enrichment CPs from water, honey, and white peach beverage samples., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Porous organic polymers have gained great research interest in the field of adsorption. A benzoxazine porous organic polymer (BoxPOP) constructed from p-phenylenediamine, 1,3,5-trihydroxybenzene and paraformaldehyde was fabricated and explored as an adsorbent for solid-phase extraction (SPE) of four chlorophenols from water and honey samples. Under the optimized SPE conditions, the response linearity for the analysis of the SPE extract of the chlorophenols by high performance liquid chromatography-diode array detector was observed in the range of 0.2-40.0 ng mL-1 for water samples and 5.0-400.0 ng g-1 for honey samples. The method detection limits of the analytes were 0.06-0.08 ng mL-1 for water samples and 1.5-2.0 ng g-1 for honey samples. The recoveries of the analytes from fortified water and honey samples ranged from 84.8 to 119.0% with the relative standard deviations below 8.4%. The results indicate that the prepared BoxPOP is an effective adsorbent for the chlorophenols. The established method provides an alternative approach for the determination of chlorophenols in real samples., (© The Author(s) 2020. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Hypercrosslinked polymers (HCPs) have demonstrated effective adsorption capabilities because of their rich porosity and high specific surface area. However, the HCPs prepared with phenylboronic acid based compounds as monomers via Friedel-Crafts alkylation reaction have not been reported yet. Herein, four new HCPs with phenylboronic acid (PBA), 1,4-benzenediboronic acid, 4-hydroxyphenylboronic acid and 4-carboxyphenylboronic acid as the respective monomers were prepared for the first time. Their Brunner-Emmet-Teller surface areas were 909.1 m 2 g -1 , 71.9 m 2 g -1 , 39.8 m 2 g -1 and 29.3 m 2 g -1 , respectively. The prepared HCP with PBA as the monomer (named as PBA-HCP) displayed the best adsorption capability for chlorophenols. Then, it was investigated as a SPE adsorbent for the extraction of some chlorophenols from water and honey-pomelo beverage samples prior to high performance liquid-phase chromatography with diode array detection. The established method had low limits of detection for the analytes in the range from 0.06 to 0.2 ng mL -1 for water samples and from 0.3 to 1.0 ng mL -1 for honey-pomelo beverage samples. The linear response for the analytes was in the range of 0.18-100.0 ng mL -1 for water samples and 0.9-100.0 ng mL -1 for honey-pomelo beverage samples. The method also had a good repeatability with the relative standard deviations less than 7.1% and a fairly good accuracy with the method recoveries falling between 80.0% and 120.0%. The adsorption capacities of the PBA-HCP for 2-chlorophenol, 3-chlorophenol, 2,3-dichlorophenol and 2,4-dichlorophenol were 21.7 mg g -1 , 31.2 mg g -1 , 77.1 mg g -1 and 82.1 mg g -1 , respectively. The PBA-HCP also exhibited excellent extraction capabilities for some other compounds, especially for those that have more hydrogen bonding 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 © 2020. Published by Elsevier B.V.)

In this study, the microcrystalline cellulose/metal-organic framework 199 hybrid (MCC/MOF-199) was applied as sorbent for the dispersive micro-solid phase-extraction (D-μSPE) of chlorophenols. The D-μSPE method combined with high-performance liquid chromatography- ultraviolet detection (HPLC-UV) was employed to determine of four chlorophenols including 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,3-dichlorophenol (2,3-DCP), and 2,5-dichlorophenol (2,5-DCP) in aqueous. The main parameters of the D-μSPE process that influence the extraction (i.e. the amount of sorbent, elution condition, extraction time, and pH) were investigated and optimized. Based on the outputs, the presence of MCC on the surface of MOF-199 leads to improve the properties of MOF-199 and the MCC/MOF-199 has the highest sorption capacity, durability, and porosity in comparison with MCC and MOF-199. According to the validation study at the optimized conditions, the linearity for the analytes was achieved in the range from 0.1 to 200 ng mL -1 for 2-CP and 4-CP and 0.15 to 200 ng mL -1 for 2,3-DCP and 2,5-DCP with correlation coefficients between 0.9928 and 0.9965. The limits of detection calculated at S/N=3 were in the range of 0.03-0.05 ng mL -1 . Besides, the relative standard deviations (RSDs) for three spiking levels (0.2, 10,100 ng mL -1 ) do not exceed 6.8% and extraction recoveries are between 81.0% and 88.3%. Finally, the D-μSPE-HPLC-UV method was successfully applied to the analysis of CPs in real water samples (mineral, river and wastewater samples) with good recoveries (95.8 to 99.5%) and satisfactory precisions (RSD < 6.8%)., 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. Published by Elsevier B.V.)

A monolithic mixed matrix membrane of functionalized multi-walled carbon nanotubes-polyethersulfone (MWCNT/PES) was prepared in a non-covalent approach and employed as an SPME fiber for extraction of chlorophenols (CPs). The proposed extraction method was followed by GC-ECD to determine the analytes. The influencing factors on the extraction efficiency such as pH, ionic strength, extraction and desorption temperature and time were studied. Under the selected conditions, calibration curves were linear over a wide concentration range from 0.005 to 1000 µgL -1 (r 2  > 0.9961) for target analytes. In addition, the limits of detection (LOD) of the method were obtained in the range of 0.3-30 ng L -1 . The relative standard deviation (RSD) for single fiber repeatability (n = 5) is from 1.4 to 4.6%. Fiber-to-fiber repeatability (n = 3) was also evaluated and the RSD is in the range of 1.3-6.3%. Applications of proposed fiber for extraction of CPs from the headspace of urine and serum samples were successfully investigated. The relative recovery in the biological samples spiked with different levels of CPs were in the range of 91.6-102.5%., 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.)

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.)

Iron dipicolinamide (Fedpa), as an efficient Fenton-like catalyst, was fabricated to excite hydrogen peroxide (H 2 O 2 ) for the removal of 2,4-dichlorophenol (2,4-DCP). The unique structures and the electronic properties of Fedpa were contributed to its excellent catalytic performance in alkaline Fenton process. Fe was chelated with dpa by four Fe-N bonds leaved two labile sites, which reduced the oxidation potential of dpa[Fe III /Fe II ], dpa[Fe V /Fe III ] or dpa[Fe IV /Fe II ] to 0.316 V and 1.189 V respectively, and made it easily be bound with H 2 O 2 to initiate the reaction. The results showed that 99.5% removal rate of 2,4-DCP (0.58 mM) was achieved by using 0.027 g/L Fedpa and 5.8 mM H 2 O 2 in 60 min at pH 9.9. The coordination between Fe and dpa enhanced the catalytic efficiency of Fe II . The active species generated in Fedpa/H 2 O 2 system contained the iron-oxo species (dpaFe V  = O or dpa IV  = O), O 2 - and HO. The iron-oxo species was the main non-radical reactive species for the degradation of 2,4-DCP and some degradation intermediates were detected by GC-QTOF. Furthermore, the influence of factors, such as Fedpa loading, solution pH, temperature and anions (F - , Cl - , SO 4 2- , NO 3 - and PO 4 3- ) on the catalytic performance of Fedpa were also discussed. This process of complexation between Fe and dpa combined with a green oxidant H 2 O 2 presents a new insight for the use of Fenton-like system in the degradation of refractory organics., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Triclosan, which is a bacteriostatic used in household items, has raised health concerns, because it might lead to antimicrobial resistance and endocrine disorders in organisms. The detection, identification, and monitoring of triclosan and its by-products (methyl triclosan, 2,4-Dichlorophenol and 2,4,6-Trichlorophenol) are a growing need in order to update current water treatments and enable the continuous supervision of the contamination plume. This work presents a customized electronic tongue prototype coupled to an electrochemical flow reactor, which aims to access the monitoring of triclosan and its derivative by-products in a real secondary effluent. An electronic tongue device, based on impedance measurements and polyethylenimine/poly(sodium 4-styrenesulfonate) layer-by-layer and TiO 2 , ZnO and TiO 2 /ZnO sputtering thin films, was developed and tested to track analyte degradation and allow for analyte detection and semi-quantification. A degradation pathway trend was observable by means of principal component analysis, being the sample separation, according to sampling time, explained by 77% the total variance in the first two components. A semi-quantitative electronic tongue was attained for triclosan and methyl-triclosan. For 2,4-Dichlorophenol and 2,4,6-Trichlorophenol, the best results were achieved with only a single sensor. Finally, working as multi-analyte quantification devices, the electronic tongues could provide information regarding the degradation kinetic and concentrations ranges in a dynamic removal treatment., Competing Interests: The authors declare no conflict of interest.

Ferrocene-based nanoporous organic polymer (Fc-NOP) was used as solid-phase extraction (SPE) adsorbent and showed excellent adsorption capacity for chlorophenols (CPs) compared with commercial C18 and multi-walled carbon nanotubes. Then, a SPE method with Fc-NOP packed cartridge combined with HPLC-UV detection was developed to determine CPs in tap water, black tea drinks and peach juice samples. Under optimal conditions, the detection limits of the method measured at the signal to noise ratio of 3 (S/N = 3) were 0.04-0.06 ng mL -1 for tap water and 0.10-0.20 ng mL -1 for black tea drinks and peach juice samples. Satisfactory method recoveries were achieved in the range of 87.6-119% with relative standard deviations of 3.11-7.83%. Result proved that this method was a sensitive and efficient method for determination of trace CPs in foods. The extraction result for more other compounds confirmed that the developed method had a great application potential for analysis of other trace pollutants in food samples., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

An amino-functionalized magnetic metal organic framework (MOF), Fe 3 O 4 -NH 2 @MIL-101(Cr), was employed for laccase immobilization for the first time. The immobilized laccase was synthesized by the adsorption and covalent binding method, thus exhibited high activity recovery, large immobilization capacity and good tolerance to low pH and high temperature conditions. The excellent stability enabled the immobilized laccase to retain 89% of its initial activity after storage for 28 days. When the ambient temperature reached 85 °C, the immobilized laccase showed 49.1% residual activity even after 6 h preservation. The stability of laccase in organic solvents such as methanol was also greatly improved. Application of the immobilized laccase for 2,4-dichlorophenol removal was also investigated. The adsorption by Fe 3 O 4 -NH 2 @MIL-101(Cr) contributed to a quick removal in the first hour, and the removal efficiency reached 87% eventually. When the reaction was completed, the immobilized laccase could be separated from the solution by a magnet. The results introduced a novel support for laccase immobilization, and the immobilized laccase had great potential in wastewater treatment., (Copyright © 2019 Elsevier Ltd. 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.)

A facile and convenient approach for the preparation of interconnected multiwalled carbon nanotube (MWCNT) monolithic sorbents in recycled plastic caps has been developed. The method, which was based on the photopolymerization of the individual MWCNTs via the formation of a W/O medium internal phase emulsion (40/60 w/w%), provides control over the size of pores, rigidity, and the mechanical stability of the final solid. Pluronic L121 was used as a surfactant containing the water phase inside it and, consequently, the organic and non-polar phase, in which the MWCNTs and the cross-linker were trapped, remained on the outside of the droplets. Optical microscopy and scanning electron microscopy (SEM) were employed to characterize the morphology of both the emulsions and the final solids, respectively. In addition, nitrogen intrusion porosimetry was performed in order to study how the specific surface area of the final monolithic solid changed (from 19.6 to 372.2 m 2  g -1 ) with the variables involved in the polymerization step. To exemplify the great sorbent potential of the synthesized material, a colorimetric assay based on the retention of methylene blue within the interconnected MWCNT monolithic structure was carried out. Finally, following the positive results, the carbon nanotube-monolithic stirred caps were applied for the determination of chlorophenols in a biological matrix such as human urine, obtaining excellent recovery values (91-98%) and good precision (5.4-9.1%) under optimized extraction conditions. Graphical abstract.

Chlorophenoxy acid herbicides (CAHs), which are widely used on cereal crops, have become an important pollution source in grains. In this work, a highly hydrophobic poly (octadecyl methacrylate-co-trimethylolpropane trimethacrylate) [poly (OMA-co-TRIM)] monolithic column has been specially prepared for hydrophobic in-tube solid-phase microextraction (SPME) of CAHs in rice grains. Due to the hydrophobicity of CAHs in acid conditions, trace CAHs could be efficiently extracted by the prepared monolith with strong hydrophobic interaction. Several factors for online hydrophobic in-tube SPME, including the length of the monolithic column, ACN and trifluoroacetic acid percentage in the sampling solution, elution volume, and elution flow rate, were investigated with respect to the extraction efficiencies of CAHs. Under the optimized conditions, the limits of detection of the four CAHs fell in the range of 0.9-2.1 μg/kg. The calibration curves provided a wide linear range of 5-600 μg/kg and showed good linearity. The recoveries of this method ranged from 87.3% to 111.6%, with relative standard deviations less than 7.3%. Using this novel, highly hydrophobic poly (OMA-co-TRIM) monolith as sorbent, a simple and sensitive online in-tube SPME-HPLC method was proposed for analysis of CAHs residue in practical samples of rice grains., Competing Interests: The authors declare no conflict of interest.

Laccases were studied for their ability to remove two compounds, 2-chlorophenol and sulfamethoxazole, in batch studies, both in buffered solutions and in wastewater samples from different points in a municipal water resource recovery facility. Two enzymes with and without a mediator (acetosyringone) were investigated: a commercial product derived from Myceliphthora thermophile and a laboratory-generated enzyme mix derived from Tramates versicolor. The chlorophenol was removed rapidly by the commercial enzyme in the presence of acetosyringone, but the primary products were coupling complexes of the reactants. Excellent removal was achieved without acetosyringone by the natural enzyme mix. Sulfamethoxazole was poorly removed in all laboratory-generated chemically buffered solutions, but was very well removed, without the addition of mediators, in secondary effluent suspensions from a municipal water resource recovery facility. Mechanistic studies are still required, but the results suggest that treatment via direct addition of enzymes is feasible to remove recalcitrant compounds in municipal wastewater., (© 2018 Water Environment Federation.)

A novel molecularly imprinted polymer coated stir bar was prepared using 2-chlorophenol (2-CP) as template molecule and used for selective extraction of phenolic compounds including chlorophenols (CPs) directly from seawater samples. Various parameters affecting extraction have been evaluated using one variable-at-a-time and Box-Behnken design. A three-level Box-Behnken experimental design by six factors, which combined the response surface methodology, was used to optimize the selective extraction of the CPs. Six independent variables, including the absorption and desorption times (ranging from 15 to 25 min), stirring speed (ranging from 550 to 650 rpm), pH of solution (ranging from 4.0 to 6.0), amount of NaCl (ranging from 0.30 to 0.40 mol/L) and temperature of extraction process (ranging from 40 to 50°C) were coded as A, B, C, D, E and F at three various levels (-1, 0 and 1). Under the optimum conditions, the detection limits calculated were 0.17, 0.33 and 0.38 μg/L, respectively, for 2-CP, 2,4-dichlorophenol and 2,4,6-trichlorophenol. The linear ranges of method were 1.0-100.0 μg/L for all CPs studied. This method was employed for the direct extraction and determination of three CPs in seawater samples.

2,4,6-Trichlorophenol (TCP) was bioelectrochemically treated in anodic and cathodic compartments of two identical dual chambered microbial fuel cells MFC-A and MFC-B under anaerobic and aerobic conditions, respectively, and energy was recovered in the form of electricity. It was observed that MFC-B with bio-cathodic treatment of TCP outcompeted the MFC-A with bio-anodic treatment. The maximum power density for MFC-A with bio-anode was found to be 446.76 mW/m 2 while for MFC-B with bio-cathode it was 1059.58 mW/m 2 . The MFC-B consistently showed higher coulombic efficiency, power density and chemical oxygen demand removal efficiency indicating the better performance of the MFC-B as compared to the MFC-A. Scanning electron micrograph also confirmed better accumulation of microbes on the anode of MFC-B and hence its better performance in terms of energy recovery. Some major genera present in the microbial community were quantified using quantitative real-time polymerase chain reaction technique. It also confirmed the dominance of electroactive species in the bio-anodic sludge of MFC-B over the bio-anodic sludge of MFC-A. Cyclic voltammogram also asserted better electrochemical activity of the bio-cathode in the treatment of chlorinated phenol toxicants in MFC-B system. The study shows that MFC can be a viable option in treatment of recalcitrant chemical compounds like TCP with the generation of energy in the form of electrical power., (Copyright © 2018 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.)

In this work, a novel core-shell structured magnetic polyimide@layered double oxides (LDO) composites coating a porous polyimide (PI)-coated Fe 3 O 4 magnetic core and layered double hydroxide (LDH) has been successfully synthesized by solve-thermal synthesis and co-precipitation process. The magnetic PI@LDO composites were characterized by scanning and transmission electron microscopy (SEM and TEM), X-ray diffraction (XRD), thermogravimetry analysis (TGA) and magnetic properties analysis. The composite materials displayed core-shell structure with flower-like morphology. The magnetic PI@LDO composites were applied to remove tetracycline (TC), 2,4-dichlorophenol (2,4-DCP) and glyphosate (GP) from aqueous solution. The action pH value was ranged from 5 to 9 for TC and GP and 3 to 7 for 2,4-DCP, respectively. Cl - showed a weak competitive adsorption effect to TC, 2, 4-DCP and GP. In addition, the presence of humic acid (HA) could slightly reduce the adsorption capacity of magnetic PI@LDO composites. The adsorption process could be well described by pseudo-second-order model for TC and GP, while pseudo-first-order model for 2,4-DCP. The experimental data of TC and 2,4-DCP could be fitted better with Freundlich model, while that of GP were fitted better with Langmuir model. The adsorptions of TC, 2,4-DCP and GP were both spontaneous and endothermic. The adsorption capacity decreased slightly after adsorption-desorption cycles repeated five times. This study demonstrated that magnetic PI@LDO exhibited great potential to be a mild and cost-effective adsorbent for the removal of various organic contaminants from wastewater., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this study, porous magnetic resin grafted chitosan (R-g-Ch) beads were prepared for removal of 4-chlorophenol and phenol from aqueous solutions. The R-g-Ch beads were characterized by vibrating sample magnetometer, Fourier-transform infrared spectroscopy, scanning electron microscopy and thermogravimetry methods. The removal of the phenolic compounds was optimized by varying the experimental conditions. Results herein are well fitted to the pseudo-second order kinetic and Langmuir isotherm. The maximum adsorption capacity of phenol and 4-chlorophenol were found to be 188.6 and 99 mg/g, respectively. The thermodynamic studies suggested that the adsorption process was exothermic, irreversible and feasible within the range of 298-318 K., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Microalgae are surprisingly efficient to remove pollutants in a hermetically closed environment, though its growth is inhibited in the absence of pollutants. The final pH, algal density, Chl-a content, and the removal efficiency of 2,4-dichlorophenol (2,4-DCP) by Chlorellar pyrenoidosa in a closed system were observed under different initial pH, lighting regimes, and various carbon sources. The optimal condition for 2,4-DCP removal was obtained, and adopted to observe the evolution of above items by domesticated and origin strains. The results showed that both respiration and photosynthesis participated in the degradation of 2,4-DCP, and caused the changes of pH. The photosynthesis seemed to increase the solution pH, while the respiration and the biodegradation of 2,4-DCP to decrease the solution pH. The domesticated strain achieved nearly 100% removal when initial concentrations of 2,4-DCP lower than 200 μg L -1 , due to providing a appropriate but narrow pH evolution range, mostly falling between 6.5 and 7.9. The research helps to understand the mechanism of biodegradation of chlorophenol compounds by green algae., (Copyright © 2018. Published by Elsevier Inc.)

Dispersive liquid-liquid microextraction (DLLME) coupled with CE was developed for simultaneous determination of five types of chlorophenols (CPs), namely 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) in water samples. Several parameters affecting DLLME and CE conditions were systematically investigated. Under the optimized DLLME-CE conditions, the five CPs were separated completely within 7.5 min and good enrichment factors were obtained of 40, 193, 102, 15, and 107 for 4-CP, 2,4,6-TCP, 2,4-DCP, 2-CP, and 2,6-DCP, respectively. Good linearity was attained in the range of 1-200 μg/L for 2,4,6-TCP, 2,4-DCP, 2-300 μg/L for 4-CP and 2-CP, and 1-300 μg/L for 2,6-DCP, with correlation coefficients (r) over 0.99. The LOD (S/N = 3) and the LOQ (S/N = 10) were 0.31-0.75 μg/L and 1.01-2.43 μg/L, respectively. Recoveries ranging from 60.85 to 112.36% were obtained with tap, lake, and river water spiked at three concentration levels and the RSDs (for n = 3) were 1.31-11.38%. With the characteristics of simplicity, cost-saving, and environmental friendliness, the developed DLLME-CE method proved to be potentially applicable for the rapid, sensitive, and simultaneous determination of trace CPs in complicated water samples., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The laccase-Cu 2 O-nanowire mesocrystal hybrid materials were developed with a superior catalytic activity inspired by natural biocatalysis processes in living cells that highly resemble the metal ions activation and the well-organized spatial structure of the natural rough endoplasmic reticulum. The enzyme and nanobiocatalyst activities of the obtained hybrid material exhibited an approximate 10-fold and 2.2-fold increase than the free enzyme, surpassing the currently available nanobiocatalysts. The comprehensive catalytic performance of the hybrid materials has been further demonstrated using a prototype continuous-flow reactor for the bioremediation of 2,4-dichlorophenol-contaminated water, which showed a high degradation efficiency and remarkable reusability. These new highly efficient nanobiocatalysts are expected to be used for diverse applications in biotechnology, biosensing, and environmental remediation.

In this study, a novel inexpensive biosorbent of pine cone powder was used for the treatment of wastewater contaminated with phenol and chlorophenols (CPhs). The biosorbent was thoroughly characterized by using CHN and BET measurements, as well as FTIR, SEM, and XRD analyses. Kinetic and equilibrium biosorption experiments showed that the uptake was more than 80% within the first 30 min of contact time at pH 5.0. The biosorption of 4-CPh onto pine cone powder was higher than those of phenol and 2-CPh. The kinetic data were consistent with the pseudo-first-order kinetic model, and the Langmuir isotherm model best represented the equilibrium data. The maximum biosorption capacities of phenol, 2-CPh, and 4-CPh were 164.51, 189.44, and 220.12 mg/g, respectively, at 30 ± 1 °C. Therefore, the pine cone powder is an effective low-cost adsorbent for the removal of phenol and CPhs from the contaminated water.

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.)

Chlorinated phenols are a class of contaminants found in water and have been regarded as a great potential risk to environment and human health. It is thus urgent to develop effective techniques to remove chlorinated phenols in wastewater. For this purpose, we employed dielectric barrier discharge (DBD) in this work and studied the efficiency of DBD for the degradation of 2,4-dichlorophenol (2,4-DCP), one of the most typical chlorophenols in the environment. The effects of pH value, applied voltage and plasma-working gases on the dichlorophenol-removal efficiency were investigated. The results demonstrate that DBD plasma could successfully degrade 2,4-DCP, achieving efficiency of 98.16% (k = 1.09 min -1 ) in the Ar-DBD system, and 77.60% (k = 0.48 min -1 ) in the N 2 -DBD system, with the process following the first-order kinetics. The removal efficiency was reduced in the presence of radical scavengers, confirming that hydroxyl radicals played a key role in the degradation process, while other active substances were also found such as nitrogen radicals in the N 2 -DBD system, which was found to have also contribution to the degradation of 2,4-DCP. The intermediates and final products generated in the degradation process were analyzed using gas chromatography-mass spectrometry (GC-MS). Based on the identification of intermediates, the degradation pathways and mechanism were proposed and discussed. Besides, the toxicity of the DBD treated 2,4-DCP solution was also assessed using GFP-expressing recombinant Escherichia coli (E. coli) as the testing organism, showing that plasma treatment could substantially reduce the toxic effect of 2,4-DCP., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A type of magnetic ionic liquid based molecularly imprinted polymer coated on SiO 2 (Fe 3 O 4 @SiO 2 @IL-MIPs) was prepared with 1-vinyl-3-ethylimidazole ionic liquid as functional monomer, and 1,4-butane-3,3'-bis-1-ethylimidazole ionic liquid as cross linker, 4-Chlorophenol as template was successfully applied as a selective adsorbent for selective extraction of 5 chlorophenols in seawater samples by using the magnetic solid-phase extraction (MSPE) method. 11 types of Fe 3 O 4 @SiO 2 @IL-MIPs were synthesized and investigated for their different compositions of functional monomer (such as [C 2 min][Br], [C 2 min][BF 4 ], [C 2 min][PF 6 ], acrylamide, methacrylic acid and 4-vinyl pyridine) and cross-linker (such as [C 4 min 2 ][Br], [C 4 min 2 ][BF 4 ], [C 4 min 2 ][PF 6 ], divinylbenzene, and ethylene glycol dimethacrylate), respectively. The [C 2 min][BF 4 ] and [C 4 min 2 ][PF 6 ] based Fe 3 O 4 @SiO 2 @IL-MIP with the highest extraction efficiencies was applied to the optimization experiment of MSPE process (including extraction time, adsorbent mass and desorption solvents). Good linearity was obtained with correlation coefficients (R 2 ) over 0.9990 and the relative standard deviations for the intra-day and inter-day determination were less than 3.10% with the extraction recoveries ranged from 85.0% to 98.4%. The results indicated that the proposed Fe 3 O 4 @SiO 2 @IL-MIPs possesses great identification and adsorption properties, and could be used as a good sorbent for selective extraction of CPs in environment waters., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A novel and efficient approach to optimization of extraction step prior the chromatographic determination of nine chlorinated phenols is described. It is based on the combination of design of experiments and multicriteria decision analysis. Such an approach is used to optimize dispersive liquid-liquid microextraction procedure for the determination of 9 chlorophenols in water samples. Three parameters are optimized - sample volume, volume of disperser solvent and extraction solvent. Combination of the technique for order of preference by similarity to ideal solution with central composite design allows to perform multi-analyte procedure optimization. It gives information about the efficiency of the system for every experimental plan point in terms of closeness to ideal solution. The optimal conditions for extraction of chlorophenols are 76 μL of extraction solvent, 0.6 mL of dispersive solvent and 6.7 mL of water sample. The presented approach has the potential to be applied in variety of optimization systems., (Copyright © 2018 Elsevier B.V. All rights reserved.)

2,4-Dichlorophenol (2,4-DCP) is considered a priority pollutant due to its high toxicity. Therefore, it is urgent to develop technologies for the disposal of this pollutant. Various remediation processes have been proposed for the elimination of 2,4-DCP in contaminated water, however, most of them involve high costs of operation and maintenance. This study aimed to determine the capacity of remediation of 2,4-DCP in water by Typha latifolia L. wild plants. For that, the tolerance, removal, accumulation and biotransformation of 2,4-DCP by T. latifolia were investigated. The plants were exposed to 2,4-DCP solutions with a concentration range from 1.5 to 300 mgL -1 for 10 days. They exhibited a reduction in chlorophyll levels and growth rate when 2,4-DCP solutions were ≥30 mgL -1 and ≥50 mgL -1 , respectively. The removal of contaminant was dose-depended, being 99.7% at 1.5-3 mgL -1 , 59-70% at 10-70 mgL -1 and 35-42% at 100-300 mgL -1 of 2,4-DCP in the solution. Studies indicated that 2,4-DCP was mainly accumulated in root tissue rather than in shoot tissue. Acid hydrolysis of biomass extracts suggests 2,4-DCP bioconjugates formation in root tissue as a response mechanism. Additionally, an increment in glutathione S-transferase (GST) activity could indicate a 2,4-DCP conjugation with glutathione as a detoxification mechanism of T. latifolia., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Presented herein is a novel headspace single drop microextraction (HS-SDME) based on temperature gradient (TG) for an on-site preconcentration technique of volatile and semivolatile samples. First, an inner vial cap was designed as a cooling device for acceptor droplet in HS-SDME unit to achieve fast and efficient microextraction. Second, for the first time, an in-vial TG was generated between the donor phase in a sample vial at 80 °C and the acceptor droplet under the inner vial cap containing cooling liquid at -20 °C for a TG-HS-SDME. Third, a simple mathematic model and numerical simulations were developed by using heat transfer in fluids, Navier-Stokes and mass balance equations for conditional optimization, and dynamic illumination of the proposed extraction based on COMSOL Multiphysics. Five chlorophenols (CPs) were selected as model analytes to authenticate the proposed method. The comparisons revealed that the simulative results were in good agreement with the quantitative experiments, verifying the design of TG-HS-SDME via the numerical simulation. Under the optimum conditions, the extraction enrichments were improved from 302- to 388-fold within 2 min only, providing 3.5 to 4 times higher enrichment factors as compared to a typical HS-SDME. The simulation indicated that these improvements in the extraction kinetics could be attributed due to the applied temperature gap between the sample matrix and acceptor droplet within the small volume of headspace. Additionally, the experiments demonstrated a good linearity (0.03-100 μg/L, R 2 > 0.9986), low limit of detection (7-10 ng/L), and fair repeatability (<5.9% RSD, n = 6). All of the simulative and experimental results indicated the robustness, precision, and usefulness of TG-HS-SDME for trace analyses of analytes in a wide variety of environmental, pharmaceutical, food safety, and forensic samples.

In this article, carbon fibres (CFs) are presented as sorbent material for the dispersive micro-solid phase extraction of twelve chlorophenols from urine samples. CFs are synthesized by a reagentless and green procedure consisting of heating raw cotton, a natural precursor, at high temperature (400°C) in an inert atmosphere (Ar) during 2h. The resulting fibres, which present good water dispersibility, are finally loaded on an in-syringe device. This device, which integrates the extraction and final elution of the analytes, is disposable and it is adapted to process low sample volumes. Working at the optimum conditions, the extraction procedure in combination with gas chromatography/mass spectrometry allows the determination of the analytes in urine at the low μg/L range. In fact, the limits of quantification (LOQs) of the analytes were in the interval from 1μg/L to 2.5μg/L with precision values, expressed as relative standard deviations (RSD), better than 13%. Relative recovery values, ranging from 74.5% to 113%, demonstrate the applicability of the proposed method., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In order to remediate organic contaminants in natural waters and soils, a novel zero-valent iron [Fe(0)]-included biochar was synthesized via slow pyrolysis. 2,4-Dinitrotoluene (DNT) and 2,4-dichlorophenol (DCP) were removed in water via sorption to the Fe(0)-included biochar. Compared to sorption control without Fe(0), the sorbed DNT and DCP were further transformed to reduction products by Fe(0)-included biochar. Compared to the reduction control with Fe(0), the presence of biochar promoted the reductive transformation of DNT and DCP. Increasing the pyrolysis temperature resulted in enhancing the removal of DNT and DCP, suggesting that the aromaticity of biochar may be responsible for the removal. The yields of the reduction products also indicated that unlike the direct reduction by Fe(0), different reduction pathways existed in the reduction of DNT and DCP with Fe(0)-included biochar. The results suggest that Fe(0)-included biochar is a viable option to immobilize and transform redox-sensitive organic contaminants in natural environments., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Regeneration of loaded adsorbents is a key step for the sustainability of an adsorption process. In this study, ozone was applied to regenerate a synthetic zeolite for the adsorption of trichlorophenol (TCP) as an organic model pollutant. Three initial concentrations of TCP in water phase were used in adsorption tests. After the equilibrium, zeolite loaded different amounts of TCP was dried and then regenerated with ozone gas. It was found that the adsorption capacity of zeolite was increased through three regeneration cycles. However, the adsorption kinetics was compromised after the regeneration with slightly declined 2nd order reaction constants. The ozone demand for the regeneration was highly dependent on the TCP mass loaded onto the zeolite. It was estimated that the mass ratio of ozone to TCP was 1.2 ± 0.3 g O3/g TCP., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The high-strength 2,4-DCP, which exists in two states: dissolved and colloidal, was studied by a continuously electro-microbial system (CEMS) and an intermittently electro-microbial system (IEMS). The hydrolysis rate of colloidal 2,4-DCP in the IEMS without electric assistance was much higher than that in the CEMS. However, the degradation rate of the dissolved 2,4-DCP and the dissolved intermediates (2-chlorophenol and 4-chlorophenol) in the IEMS without electric assistance were much lower than that in the CEMS. By adjusting the intermittent operation mode, the degradation time of 2,4-DCP was shortened greatly. Microbial characteristics in the CEMS and the IEMS were different. The correlation analysis for the main factors affecting the hydrolysis was performed by SPSS, and it was found that the correlation coefficient (rp) was -0.912 for extracellular polymeric substances (EPS) content, 0.823 for zeta potential and 0.632 for relative hydrophobicity, respectively., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A novel magnetic porous carbon derived from a bimetallic metal-organic framework, Zn/Co-MPC, was prepared by introducing cobalt into ZIF-8. Magnetic porous carbon that possesses magnetic properties and a large specific surface area was firstly fabricated by the direct carbonization of Zn/Co-ZIF-8. The prepared magnetic porous carbon material was characterized by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, N2 adsorption, and vibrating sample magnetometry. The prepared magnetic porous carbon was used as a magnetic solid-phase extraction adsorbent for the enrichment of chlorophenols from water and honey tea samples before high-performance liquid chromatography analysis. Several experimental parameters that could influence the extraction efficiency were investigated and optimized. Under the optimum conditions, good linearities (r > 0.9957) for all calibration curves were obtained with low limits of detection, which are in the range of 0.1-0.2 ng mL(-1) for all the analytes. The results showed that the prepared magnetic porous carbon had an excellent adsorption capability toward the target analytes., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study proposes a new technique to treat waste air containing 2-Chlorophenol (2-CP), namely an integrated process coupling absorption of the compound in an organic liquid phase and its enzymatic degradation. Silicone oil (47V20) was used as an organic absorbent to allow the volatile organic compound (VOC) transfer from the gas phase to the liquid phase followed by its degradation by means of Cross-linked Brassica rapa peroxidase (BRP) contained in the organic phase. An evaluation of silicone oil (47V20) absorption capacity towards 2-CP was first accomplished by determining its partition coefficient (H) in this solvent. The air-oil partition coefficient of 2-CP was found equal to 0.136 Pa m(3) mol(-1), which is five times lower than the air-water value (0.619 Pam(3) mol(-1)). The absorbed 2-CP was then subject to enzymatic degradation by cross-linked BRP aggregates (BRP-CLEAs). The degradation step was affected by four parameters (contact time; 2-CP, hydrogen peroxide and enzyme concentrations), which were optimized in order to obtain the highest conversion yield. A maximal conversion yield of 69% and a rate of 1.58 mg L(-1) min(-1)were obtained for 100 min duration time when 2-CP and hydrogen peroxide concentrations were respectively 80 mg L(-1) and 6 mM in the presence of 2.66 UI mL(-1) BRP-CLEAs. The reusability of BRP-CLEAs in silicone oil was assessed, showing promising results since 59% of their initial efficiency remained after three batches., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

In this study, coarse sand-supported zero valent iron (ZVI) composite was synthesized by adding sodium alginate to immobilize. Composite was detected by scanning electron microscope (SEM), X-ray diffraction (XRD), and X-ray fluorescence (XRF). SEM results showed that composite had core-shell structure and a wide porous distribution pattern. The synthesized composite was used for degradation of 2,4-dichlorophenol (2,4-DCP) contamination in groundwater. Experimental results demonstrated that degradation mechanism of 2,4-DCP using coarse sand-supported ZVI included adsorption, desorption, and dechlorination. 2,4-DCP adsorption was described as pseudo-second-order kinetic model. It was concluded that dechlorination was the key reaction pathway, ZVI and hydrogen are prime reductants in dechlorination of 2,4-DCP using ZVI.

This study details the application of naturally available biogenic substrates (NABS) in microbial degradation of 2-chlorophenol (CP). Jatropha deoiled cakes (JDC) and Karanja deoiled cakes (KDC) are used as NABS. The potential of NABS is compared with standard biogenic substrate, glucose. The study was carried out with both acclimatized mixed culture and pure culture, Pseudomonas putida. Microbial activity of the culture was monitored by measuring reduction in chlorophenol concentration, COD, toxicity and Cl(-) ions evolution. The study was carried out for a total of 42days. It was observed that culture having NABS has shown similar chlorophenol reduction but higher COD and toxicity reduction. Amongst NABS, Jatropha deoiled cake (JDC) has shown superior results of 71% COD reduction compared to glucose and KDC. This study is one of the first kind illustrating the potential of these substrates in removing toxic chemicals from wastewaters., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Solid-liquid extraction, ultrasonic-assisted extraction and matrix solid-phase dispersion (MSPD) were optimized and compared in terms of recoveries for the simultaneous extraction of indole (IND) and 2,4-dichlorophenol (DCP) from catfish samples and for the extraction of IND alone from potato samples. Applying high-performance liquid chromatography (HPLC-DAD) procedure using mobile phase of methanol : water (65 : 35) at 280 nm, MSPD was the method of choice for the extraction of IND and DCP from catfish and, also, for IND from potato. The extraction recoveries of MSPD were in the range (97.9-99.7%) and (99.8-100.6%); for IND and DCP, respectively, in catfish samples and (98.4-99.7%) for IND alone in potato samples. Solid-phase extraction (SPE) was chosen the method of choice for the extraction of DCP from fish farms water samples after optimization and comparison with direct sample injection and extraction recoveries were in the range (97.9-100.3%). Kinetics were further studied to follow each of production of IND in catfish during storage at different temperatures and uptake of DCP by tilapia in fish farms water samples using MSPD-HPLC and SPE-HPLC, respectively., (© The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

A photosensitizer tetra-α-(2,4-di-tert-butylphenoxy)-phthalocyaninato zinc [ZnPc(OAr)4] was successfully encapsulated in SiO2 nanoparticle by the microemulsion method. The photosensitized composite nanoparticle was able to degrade 2,4,6-trichlorophenol (TCP) in aqueous solution. Under visible light irradiation, the nanoparticles efficiently generated reactive oxygen species; 95.4% of TCP was degraded after 270 min of reaction. Some aromatic compounds and aliphatic carboxylic acids were detected by mass spectrometry as the reaction intermediates. The results were different from those of previously reported photocatalytic reactions, in which valence band holes or hydroxyl radicals functioned as the main oxidants. The photosensitizing composite nanoparticle is potentially applicable to the oxidation of phenol.

The aim of this study was to contribute to the knowledge on the dynamic of the microbial community involved in anaerobic degradation of different concentrations of 2-chlorophenol (2CP, from 28 to 196 mg 2CP-C/L) and a mixture of 2CP and phenol (from 28 to 196 mg phenol-C/L) and its relationship with the respiratory process in two anaerobic sequencing batch reactors (ASBR). The dynamic of the microbial community was evaluated by denaturant gradient gel electrophoresis (DGGE) and ecological indices (S and J indices). The respiratory process was evaluated by means of substrate consumption efficiency, biogas yield, and specific consumption rates as response variables. The high consumption efficiency (90%) and the constant biogas yields obtained at concentrations up to 140 mg C/L may be related with the evenness of microbial populations (J index=0.97±0.2) present in both reactors. Pseudomonas genus was present in all concentrations tested, suggesting a possible relationship with the dehalogenation observed in both reactors. The decrease in specific consumption rate and biogas yield as well as the accumulation of phenol and volatile fatty acids observed in both reactors at 196 mg 2CP-C/L might be associated with the disappearance of the bands related to Caulobacter and Bacillus. At these conditions, the disappearance of fermentative or acetogenic bacteria resulted in reduction of substrates required to carry out methanogenesis, which eventually might cause the declination in methanogenic populations present in the reactors.

A rapid and sensitive electrochemical sensor based on disulfides bridged β-cyclodextrin dimer-functionalized multi-walled carbon nanotube (DBβ-CD-MWCNT) nanohybrids with higher supramolecular recognition capability was successfully constructed for the first time. Simultaneous trace analysis of three phenols (4-aminophenol, 4-AP; 4-chlorophenol, 4-CP; 4-nitrophenol, 4-NP) in tap-water and wastewater samples was performed based on the constructed sensor. Cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy were utilized to characterize the properties of the modified electrode. The proposed DBβ-CD-MWCNT-modified electrode displayed electrochemical signal superior to those of β-CD-MWCNT and MWCNT towards 4-AP, 4-CP, and 4-NP. Under optimal conditions, differential pulse voltammetry was used to simultaneously quantify 4-AP, 4-CP, and 4-NP within the concentration range of 0.01-20, 0.1-200, and 0.1-200 µM, respectively. The detection limits (S/N=3) of the DBβ-CD-MWCNT nanohybrid electrode for 4-AP, 4-CP, and 4-NP were 0.0042, 0.028, and 0.048 µM, respectively. Satisfactory results revealed that this proposed electrochemical sensor can provide a promising candidate for the simultaneous trace analysis of 4-AP, 4-CP, and 4-NP in environmental monitoring of water and wastewater samples. The present work might broaden the channel toward the application of bridged CD in the electrochemical sensing or biosensing., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Eleven new polyphenols namely spiromastols A-K (1-11) were isolated from the fermentation broth of a deep sea-derived fungus Spiromastix sp. MCCC 3A00308. Their structures were determined by extensive NMR data and mass spectroscopic analysis in association with chemical conversion. The structures are classified as diphenyl ethers, diphenyl esters and isocoumarin derivatives, while the n-propyl group in the analogues is rarely found in natural products. Compounds 1-3 exhibited potent inhibitory effects against a panel of bacterial strains, including Xanthomanes vesicatoria, Pseudomonas lachrymans, Agrobacterium tumefaciens, Ralstonia solanacearum, Bacillus thuringensis, Staphylococcus aureus and Bacillus subtilis, with minimal inhibitory concentration (MIC) values ranging from 0.25 to 4 µg/mL. The structure-activity relationships are discussed, while the polychlorinated analogues 1-3 are assumed to be a promising structural model for further development as antibacterial agents.

The determination and remediation of three phenolic compounds bisphenol A (BPA), ortho-nitrophenol (o-NTP), parachlorophenol (PCP) in wastewater is reported. The analysis of these molecules in wastewater was done using gas chromatography (GC) × GC time-of-flight mass spectrometry while activated carbon derived from maize tassel was used as an adsorbent. During the experimental procedures, the effect of various parameters such as initial concentration, pH of sample solution, eluent volume, and sample volume on the removal efficiency with respect to the three phenolic compounds was studied. The results showed that maize tassel produced activated carbon (MTAC) cartridge packed solid-phase extraction (SPE) system was able to remove the phenolic compounds effectively (90.84-98.49%, 80.75-97.11%, and 78.27-97.08% for BPA, o-NTP, and PCP, respectively). The MTAC cartridge packed SPE sorbent performance was compared to commercially produced C18 SPE cartridges and found to be comparable. All the parameters investigated were found to have a notable influence on the adsorption efficiency of the phenolic compounds from wastewaters at different magnitudes.

A novel magnetic three-dimensional graphene nano-composite (3D-G@Fe3O4) with a high surface area was synthesised by a vacuum freeze-dried method. Due to its high surface area, specific 3D nanoporous structure and excellent magnetic properties, it can be used as a magnetic solid-phase extraction adsorbent. Some chlorophenols in a honey samples were enriched by this nanocomposite prior to their determination by HPLC with ultraviolet detection. Factors that affect the extraction efficiency, such as the amount of 3D-G@Fe3O4, extraction time, sample pH, ionic strength and desorption conditions, were investigated and optimised. Under the optimum conditions, good linearity existed in the range of 10.0-1000.0 ng g(-1). The enrichment factors of the method for the analytes were in the range from 101 to 248. The limits of detection of the method (S/N = 3) were 1.0-1.5 ng g(-1). The recoveries of the method for the analytes at spiking levels of 100.0 and 400.0 ng g(-1) were in the range of 93.2-98.9%. The results showed that the proposed method is simple, reliable and sensitive. It will be a useful tool for the routine monitoring of chlorophenols in honey products.

Asparagus byproducts are a good source of cationic soluble peroxidases (CAP) useful for the bioremediation of phenol-contaminated wastewaters. In this study, cell wall bound peroxidases (POD) from the same byproducts have been purified and characterized. The covalent forms of POD represent >90% of the total cell wall bound POD. Isoelectric focusing showed that whereas the covalent fraction is constituted primarily by anionic isoenzymes, the ionic fraction is a mixture of anionic, neutral, and cationic isoenzymes. Covalently bound peroxidases were purified by means of ion exchange chromatography and affinity chromatography. In vitro detoxification studies showed that although CAP are more effective for the removal of 4-CP and 2,4-DCP, anionic asparagus peroxidase (AAP) is a better option for the removal of hydroxytyrosol (HT), the main phenol present in olive mill wastewaters.

This study presents a new technique, dispersive micro solid phase extraction (DMSPE) combined with headspace solid phase micro-extraction (HS-SPME) for extraction and determination of chlorophenols (CPs) in water and honey samples using a Gas Chromatography-Electron Capture Detector (GC-ECD). Zein nanoparticles were made by liquid-liquid dispersion and applied for the first time as the sorbent phase in DMSPE. In the proposed DMSPE-HS-SPME method, 1% w/v of ethanolic zein solution was added to an aqueous sample and then a dose of the in-situ generated zein nanoparticles was applied to a pre-concentration of target analytes. Thermal desorption of analytes was performed after the isolating sorbent phase, and then HS-SPME was applied for enrichment prior to introducing to gas chromatography. All the important parameters influencing efficiency of the extraction process such effects of salt, pH, sorbent concentration, temperature, sorbent solution volume in DMSPE procedure, extraction temperature, extraction time, desorption temperature and time in the HS-SPME procedure were investigated and optimized. Results showed that under optimum extraction conditions, detection limits (signal to noise ratio=3) were in the range of 0.08-0.6 ng mL(-1) and evaluations for relative standard deviations (RSDs %) were between 6.62% and 8.36%., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A vortex assisted liquid-liquid microextraction (VALLME) method was developed and optimised for the determination of the main compounds that can cause cork taint in wines, 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), 2,4,6-tribromoanisole (TBA) and pentachloroanisole (PCA); and their corresponding halophenolic precursors. Target compounds were determined by gas chromatography combined with a micro-electron capture detector (GC-µECD) system. Halophenol extraction and derivatisation processes were performed at the same time. To optimise the VALLME method, the extraction solvent was selected. Then, the other parameters of influence, such as volume of extraction solvent and derivatisation agent, salt addition and vortex time were optimised using a central composite design combined with desirability functions. Once the optimal conditions had been determined, the method was validated, showing satisfactory linearity (with correlation coefficients over 0.983), repeatability (below 10.0%) and reproducibility (below 11.2%). Detection limits obtained were lower than the olfactory threshold of the studied compounds, being similar or even lower than previously reported with the advantage of reducing the extraction time. The analysis of real wine samples demonstrated the applicability of the method. To our knowledge, this is the first time that VALLME has been applied for the simultaneous determination of haloanisoles and halophenols in wine., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A method based on the coupling of in situ extraction and derivatization of chlorophenols (CPs) (2-chlorophenol, 4-chloro-3-methylphenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol) from soils, accomplishing their preconcentration by means of automated microextraction by packed sorbent (MEPS), is proposed. After extraction and acylation of the chlorophenols in aqueous medium, the liquid phase obtained is subjected to the MEPS procedure. The QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and MEPS techniques were compared and the results confirmed the preconcentration carried out with MEPS. The existence of a matrix effect was checked and the analytical characteristics of the method were determined in a soil sample. The method provided good linearity (from 1 to 12μgkg(-1)), together with good repeatability and reproducibility values (RSD equal to or less than 10%). The limits of detection were in the 0.118-0.894μgkg(-1) range. A certified reference material was applied to validate the proposed methodology., (Copyright © 2014 Elsevier B.V. All rights reserved.)