A magnetically induced self-assembly of Ru@Fe3O4/rGO cathode for diclofenac degradation in electro-Fenton process.

In this study, a novel magnetic nanocomposite of Ru@Fe3O4/rGO was successfully synthesized by a simple hydro-thermal method. The Ru@Fe3O4/rGO particles were assembled and immobilized for innovative magnetically assembled electrode (MAE) without any binder, and the electrode was further applied in heterogeneous electro-Fenton (hetero-EF) process for the degradation of diclofenac (DCF). The results showed that rGO could remarkably enhance the conductivity and catalyze the two-electron oxygen reduction, which greatly improved the generation of H2O2. In addition, the mixture valence of Fe and Ru species might provide rich reaction sites and enhance electron transfer by synergy. Thus, the Ru@Fe3O4/rGO MAE exhibited a stable and high electrocatalytic activity in the hetero-EF process for DCF degradation over a wide pH range from 2 to 9 owing to the higher electroactive surface area (EASA) and lower charge/mass-transfer resistance. The DCF degradation efficiency could reach about 100% within 90 min under pH 5 and current 40 mA, and the Ru@Fe3O4/rGO MAE showed high stability and reusability after five cycles. Theoretically, 1O2 and •OH were the main reactive oxygen species (ROS) participating in DCF degradation in the Ru@Fe3O4/rGO MAE hetero-EF process. Furthermore, according to the LC-MS/MS intermediates, the possible DCF degradation pathway was deduced including dechlorination, hydroxylation and ring opening attacked by ROS. Eleven intermediates were detected during DCF degradation in the MAE hetero-EF process, and the ecological risk of DCF degradation in Ru@Fe3O4/rGO MAE hetero-EF process was significantly reduced. This study provides new insights into the magnetically assembled electrode of Ru@Fe3O4/rGO and displays a new practical application prospect of the materials for high-efficient removal and degradation of DCF from wastewater.

Facile Phase Control and Photocatalytic Performance of BiVO4 Crystals for Methylene Blue Degradation.

Emerging contaminants, which mainly exist as organic pollutants and pose adverse biological effects, could be removed using photocatalytic degradation, resulting in a low-cost and environmentally friendly solution. Herein, BiVO4 nanoparticles with different morphologies and photocatalytic performances were synthesized by hydrothermal treatment at different residence times. The XRD and SEM results indicate that the crystal phase of BiVO4 gradually transformed from a single tetragonal phase to a single monoclinic crystal phase as the hydrothermal time increased, and with the extension of the hydrothermal time, the morphology of BiVO4 nanoparticles gradually differentiated from a smooth spherical shape to flower-like shapes composed of polyhedrons; the size of the crystals also increased accordingly. Methylene blue (MB), used as a probe of organic pollutants, was degraded under visible light irradiation by all BiVO4 samples to investigate its photocatalytic activities. The experimental results show that the longer the hydrothermal time, the better the photocatalytic performance. The optimum hydrothermal time was 24 h, at which the sample showed the highest photocatalytic activity for MB degradation. This work shows a convenient strategy for control of the crystal phase of BiVO4-based photocatalysts based on the understanding of the crystal morphology evolution mechanism, which will benefit the researchers in designing new BiVO4-based photocatalysts with high efficiency for emerging contaminants' degradation.

Insights into enhanced peroxydisulfate activation with S doped Fe@C catalyst for the rapid degradation of organic pollutants.

In this study, the S modified iron-based catalyst (S-Fe@C) for activating peroxydisulfate (PDS) was fabricated by heating the S-MIL-101 (Fe) precursor at 800 °C. The resulted S-Fe@C composite mainly consisted of carbon, Fe0, FeS, FeS2, and Fe3O4, and showed strong magnetism. Compared with Fe@C obtained from MIL-101 (Fe), the S-Fe@C exhibited much higher performance (1.5 times larger) on PDS activation and the S-Fe@C/PDS could rapidly degrade various organic pollutants in 5 min under the attack of the species of SO4-·, 1O2, electro-transfer and Fe(IV). The S element in enhancing the PDS activation mainly involved two mechanisms. Firstly, the doped S could speed up the electron transfer efficiency, resulting in a promotion on PDS decomposition; secondly, the S2- S22- or S0 could achieve the circulation of Fe2+ and Fe3+, leading to the formation of non-radicals Fe(IV) and 1O2.

Phenanthrene degradation in soil using biochar hybrid modified bio-microcapsules: Determining the mechanism of action via comparative metagenomic analysis.

A strategy involving biochar (BC) hybrid modification was developed to promote the bioremediation effect of degrading bacteria immobilized in layer-by-layer assembly (LBL) microcapsules for the treatment of phenanthrene (PHE) polluted soil. A taxonomic and functional metagenomic approach was used to investigate changes in the microbial community structures and functional gene compositions in the PHE-polluted soil during the bioremediation process. Biofortification with an initial PHE concentration of 100 mg kg-1 dry soil in soils using the BC (3%) hybrid LBL bio-microcapsule (BC-LBL, 2.0 g kg-1 dry soil, 107 colony forming unite cell g-1 dry soil) was faster; further, a higher PHE degradation efficiency (80.5% after 25 d) was achieved when compared with that by the LBL agent (66.2% after 25 d) used. Sphingomonas, Streptomyces, Gemmatirosa, Ramlibacter, Flavisolibacter, Phycicoccus, Micromonospora, Acidobacter, Mycobacterium and Gemmatimonas were more abundant in BC-LBL treatment than those in LBL one. Functional gene annotation results showed that more gene number with BC-LBL treatment than those with LBL one. More abundant functions in the former were primarily related to the growth, reproduction, metabolism, and transportation of bacteria. BC hybridization promoting PHE degradation by microencapsulated bacteria may be due to the strong adsorption property of BC, which results in the enrichment of the nutrients that needed for bacterial growth and reproduction, as well as enhancing the mass transfer performance of PHE to BC-LBL; Meanwhile, BC could also stimulate and improve the metabolism and membrane transportation of the degrading bacteria, and finally improving the degradation function.

Bacterial communities and functional genes stimulated during phenanthrene degradation in soil by bio-microcapsules.

In this study, a taxonomic and functional metagenomic method was used to investigate the difference produced between degrading bacteria immobilized in layer-by-layer assembly (LBL) microcapsules or not during the bioremediation of a soil polluted with phenanthrene (PHE). Bioaugmentation with LBL microcapsule immobilized degrading bacteria could result in different changes of native microbial communities, shifting the functional gene constructions of polluted soils. The LBL treatment enhanced PHE degradation (initial concentration of 100 mg kg-1 dry soil) by 60% after 25 d compared to the free bacteria (FB). The enhancing effect of PHE degradation produced by the LBL treatment was found to be significantly associated with some crucial phyla (e.g., Bacteroides, Gemmatimonadetes and Acidobacteria) and genera including Streptomyces, Ramlibacter, Mycobacterium, Phycicoccus, Gemmatirosa, Flavisolibacter, Micromonospora, Acid_Candidatus_Koribacter and Gemmatimonas. The main differences of functional metagenomics between LBL and FB treatments were observed in higher levels in metabolism of aromatic hydrocarbons and its related functions or enzymes in the former, e.g., membrane transport systems, binding, substrate transporter, cleavage enzymes, dehydrogenation, oxidase, esterase and glycosidase, greatly favoring PHE mineralization. Therefore, our results provide useful findings on understanding of how immobilization strategies can influence the taxonomic and functional gene composition in soils, as well as polycyclic aromatic hydrocarbons (PAH) degradation.

Synthesis of silica-composited biochars from alkali-fused fly ash and agricultural wastes for enhanced adsorption of methylene blue.

Two types of silica-composited biochars were prepared by mixing swine manure or rice straw with alkali-fused fly ash (AFFA) followed by pyrolysis. A 10% (w/w) AFFA modification improved the specific surface area, pore volume, and average pore size of the biochars. Certain surface oxygen-containing functional groups (i.e., -OH and CO) in the biochars were protected, and silicon-oxygen bonds (i.e., O-Si-O and OSi) were strengthened considerably by AFFA modifications during high-temperature pyrolysis. The adsorption capacity of biochar for methylene blue (MB) was enhanced after AFFA modification, and a modified biochar with the highest adsorption capacity was prepared at a pyrolysis temperature of 700 °C, pyrolysis holding time of 2 h, and an AFFA proportion of 10%. The MB adsorption capacity of the modified biochars significantly increased when the pH of the solution increased (from 3 to 13). The adsorption data were well described by a pseudo-second-order model and Langmuir isotherms. The maximum MB adsorption capacities of the modified swine manure and rice straw biochars were 143.76 mg/g and 131.58 mg/g, respectively. The adsorption capacities of the AFFA-modified biochars were 10.7-112.3% higher than those of the unmodified biochars. The enhanced MB adsorption capacities of the former appear to be attributed to their increased specific surface areas, increased porosities, strong oxygen-containing functional groups, and high contents of exchangeable sodium ions. These results indicate that industrial and agricultural wastes can be reused to produce novel silica-composited biochars with high MB removal capacity. Accordingly, these biochars could be effectively used to treat wastewater and thus to mitigate solid waste disposal-related problems.

Contamination of pyrethroids in agricultural soils from the Yangtze River Delta, China.

This study focused on contamination levels and spatial distributions of four common pyrethroids found in agricultural soils of the Yangtze River Delta (YRD), China. Pyrethroids were detected in 241 soil samples (88.8% detection rate) with total concentrations ranging from  cypermethrin (1.10 ng/g) > deltamethrin (0.89 ng/g) > cyhalothrin (0.20 ng/g). The highest concentration of fenpropathrin was recorded as 37.6 ng/g. The highest detection rate of 63.9% was found for cyhalothrin. A distinct pattern of spatial distribution was observed where high concentrations of pyrethroids were detected in sites around Taihu Lake. Potential sources of pyrethroids in agricultural soils from the YRD region include pyrethroids used for pest control and wastewater irrigation in the region. Redundancy and correlation analyses show that the soil TOC values have played a significant role in the behavior of pyrethroids in agricultural soils of the YRD region. Potential ecological risks of pyrethroids in agricultural soils of the YRD region are low. Cypermethrin and cyhalothrin showed potential toxic effects on the ecological conditions of agricultural soils in 4.6% and 2.9% of the sampling sites, respectively. Further studies should pay more attention to the potential human health risks posed by pyrethroids in agricultural soils for the protection of soil quality and food safety.

Contamination of pyrethroids and atrazine in greenhouse and open-field agricultural soils in China.

A national-scale survey was conducted to assess the levels and distribution of two extensively used pesticides (pyrethroids and atrazine) in greenhouse and open-field soils in 20 provinces across China. Concentrations between 1.30 and 113 ng/g and 0.51-85.4 ng/g for the total pyrethroids (PYs) and of LOD-137 ng/g and LOD-134 ng/g for atrazine were found in greenhouse and open-field soils, respectively. Higher contaminations were found in the greenhouse than in the open fields. The levels of total pyrethroids in 80% of the greenhouses and of atrazine in 60% of the greenhouses were significantly higher than those in the nearby open-field soils (p < 0.05), respectively. The contamination of PYs and atrazine was generally more serious in the northern provinces of China, such as Heilongjiang, Jilin, Liaoning, Beijing, and Hebei. Pearson correlation analysis revealed that the contamination of PYs was significantly correlated with the soil total organic carbon (TOC) value in both greenhouse and open-field soils. Canonical correspondence analysis (CCA) showed that PYs might have an impact on the microbial alpha diversity, while cyhalothrin and cypermethrin may be the key factors affecting the microbial community in the greenhouse and open-field soils. The soil samples containing pesticide residues showed distinct taxonomic and functional communities, where an increased diversity and abundance of microorganisms able to degrade pesticides was observed with high-level PYs contamination. These findings provide useful information for evaluating PYs and atrazine pollution and for contamination management in greenhouse agriculture.

Mechanism of enhancing pyrene-degradation ability of bacteria by layer-by-layer assembly bio-microcapsules materials.

The mechanism of improving pyrene (PYR)-degrading ability of bacteria CP13 in Layer-by-layer (LBL) assembly chitosan/alginate (CHI/ALG) bio-microcapsules was investigated. Flow cytometry analysis showed that LBL microcapsules could effectively slow down the increasing rate of bacterial cell membrane permeability and the decreasing rate of the membrane potential, so as to reduce the death rate and number of the cells, which could protect the degrading bacteria. The results of Fluorescence spectrum, circular dichroism (CD) spectrum and laser light scattering (LLS) analysis revealed that the other possible mechanism for LBL microcapsules to promote bacterial degradation were following: CHI could enter the secondary structure of the protein of the extracellular polymeric substances (EPS) from CP13 and combined with EPS to generate a stable ground material, which had larger molecular weight (3.76×106 g mol-1) than the original EPS (2.52×106 g mol-1). The combination of CHI and EPS resulted in the decrease of the density of EPS from 1.18 to 0.72 g L-1, suggesting that CHI can loosen the EPS configurations, improving the capture ability of bacteria for PYR as well as the mass transfer of PYR from the extracellular to intracellular, thus eventually promoting the bacteria degrade performance.

The transformation of triclosan by laccase: Effect of humic acid on the reaction kinetics, products and pathway.

This study systematically explored the effect of humic acid (HA) (as model of natural organic matter) on the kinetics, products and transformation pathway of triclosan (TCS) by laccase-catalyzed oxidation. It was found that TCS could be effectively transformed by laccase-catalysis, with the apparent second-order rate constant being 0.056 U-1 mL min-1. HA inhibited the removal rate of TCS. HA-induced inhibition was negatively correlated with HA concentration in the range of 0-10 mg L-1 and pH-dependent from 3.5 to 9.5. FT-IR and 13C NMR spectra showed a decrease of aromatic hydroxyl (phenolic) groups and an increase of aromatic ether groups, indicating the cross-linking of HA via C-O-C and C-N-C bonds during enzyme-catalyzed oxidation. Ten principle oxidative products, including two quinone-like products (2-chlorohydroquinone, 2-chloro-5-(2,4-dichlodichlorophenoxy)-(1,4)benzoquinone), one chlorinated phenol (2,4-dichlorophenol (2,4-DCP)), three dimers, two trimmers and two tetramers, were detected by gas chromatograghy/mass spectrometry (GC-MS) and high performance liquid chromatography/quadrupole time-of-flight/mass spectrometry (HPLC/Q-TOF/MS). The presence of HA induced significantly lesser generation of self-polymers and enhanced cross-coupling between HA and self-polymers via C-O-C, C-N-C and C-C coupling pathways. A plausible transformation pathway was proposed as follows: TCS was initially oxidized to form reactive phenoxyl radicals, which self-coupled to each other subsequently by C-C and C-O pathway, yielding self-polymers. In addition, the scission of ether bond was also observed. The presence of HA can promote scission of ether bond and further oxidation of phenoxyl radicals, forming hydroxylated or quinone-like TCS. This study shed light on the behavior of TCS in natural environment and engineered processes, as well provided a perspective for the water/wastewater treatment using enzyme-catalyzed oxidation techniques.

Selective removal and preconcentration of triclosan using a water-compatible imprinted nano-magnetic chitosan particles.

A water-compatible magnetic triclosan (TCS) imprinted material (TCS-CTS-Fe0-MIPs) was synthesized for selective enrichment and detection of TCS in real complex water samples. The material was synthesized by using chitosan (CTS) as functional monomer, which has rich surface O- and N-containing functional groups. The TCS imprinted CTS was coated on Fe0 surface and then cross-linked with glutaraldehyde. Scanning electron microscopy suggested that the imprinted material was covered with a layer of imprinted film, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirmed that the imprinted material had more functional groups (amino and hydroxyl groups) than that of non-imprinted material. The TCS imprinted and non-imprinted materials used in each adsorption experiments were 0.1 mg mL-1. The maximum adsorption capacity of the TCS imprinted material and non-TCS imprinted material were 20.86 and 15.11 mg g-1, respectively. The adsorption results showed that selectivity coefficient was 10.151, 1.353, and 8.271 in the presence of p-chlorophenol, 2,4,6-trichlorophenol, and bisphenol-A, respectively. The recoveries of river water and lake water samples were 92.8, 91.3, 92.4, and 81.4, 82.3, 82.1%, respectively, when the samples were spiked with 4, 6, and 8 µg L-1 of TCS with the imprinted material. The adsorption capacity of the TCS imprinted material and non-TCS imprinted material lost 5.2 and 6.2% after six times of recycling. The high selectivity and excellent adsorption capacity of the imprinted material can be attributed to the presence of sterically complementary imprinted sites and high surface, which would also made it more accessible to TCS than that of non-imprinted material. The present study would provide an environmental friendly and convenient method for the removal and the monitoring of TCS in environmental water samples.

High efficiency removal of triclosan by structure-directing agent modified mesoporous MIL-53(Al).

In order to expand the potential applications of metal-organic frameworks (MOFs), structure directing agents modified mesoporous MIL-53(Al) (MIL-53(Al)-1) was investigated to adsorb triclosan (TCS) with two different initial concentrations. MIL-53(Al)-1 with high mesoporosity and total pore volume exhibited higher adsorption capacity and 4.4 times faster adsorption of TCS at low concentration (1 mg L-1) than that of microporous MIL-53(Al). Also, mesoporous as well as microporous MIL-53(Al) showed significant higher adsorption capacity and two orders of magnitude greater fast uptake of TCS than two kinds of mesoporous-activated carbon. The adsorption of TCS onto MIL-53(Al)-1 released more energy and had higher disorderliness than TCS on MIL-53(Al). The superior adsorption characteristics of MIL-53(Al)-1 were preserved over a wide pH range (4-9), at high concentration of ionic strengths, and in the presence of coexisting compounds (anions, cations, phenol, aniline, and humic acid). The selectivity adsorption and Fourier transform infrared (FT-IR) spectra revealed that TCS adsorption on MIL-53(Al)s was mainly driven by hydrophobicity interaction assisted with hydrogen bonding on MIL-53(Al)s. MIL-53(Al)s can be effectively regenerated several times by washing with 90% methanol-water (pH 11). All of the above results demonstrated MIL-53(Al)s are promising adsorbents for water purification. Graphical abstract.

Treatment of Ni-EDTA containing wastewater by electrocoagulation using iron scraps packed-bed anode.

The unique electrocoagulator proposed in this study is highly efficient at removing Ni-EDTA, providing a potential remediation option for wastewater containing lower concentrations of Ni-EDTA (Ni ≤ 10 mg L-1). In the electrocoagulation (EC) system, cylindrical graphite was used as a cathode, and a packed-bed formed from iron scraps was used as an anode. The results showed that the removal of Ni-EDTA increased with the application of current and favoured acidic conditions. We also found that the iron scrap packed-bed anode was superior in its treatment ability and specific energy consumption (SECS) compared with the iron rod anode. In addition, the packed density and temperature had a large influence on the energy consumption (ECS). Over 94.3% of Ni and 95.8% of TOC were removed when conducting the EC treatment at an applied current of 0.5 A, initial pH of 3, air-purged rate 0.2 L min-1, anode packed density of 400 kg m-3 temperature of 313 K and time of 30 min. SEM analysis of the iron scraps indicated that the specific area of the anode increased after the EC. The XRD analysis of flocs produced during EC revealed that hematite (α-Fe2O3) and magnetite (Fe3O4) were the main by-products under aerobic and anoxic conditions, respectively. A kinetic study demonstrated that the removal of Ni-EDTA followed a first-order model with the current parameters. Moreover, the removal efficiency of real wastewater was essentially consistent with that of synthetic wastewater.

[Toxicities of 30 ionic liquids to Vibrio qinghaiensis sp. Q67].

To systematically and effectively assess the toxic effects of "green solvent" ionic liquid (ILs) to a novel freshwater luminescent Vibrio qinghaiensis sp. Q67 (Q67), the toxicities of 30 ILs with different alkyl chain lengths, anions and cation skeletons (methylimidazolium, dimethylimidazolium and pyridinium) were determined using the microplate toxicity analysis. The observed dose-response curves (DRCs) were fitted by using the nonlinear least square regression. It was shown that the DRCs of 30 ILs could be well described by the Logit or Weibull function (R > 0.98, RMSE < 0.053). The toxicities of 30 ILs varied greatly and the pEC50 values of 30 ILs ranged from 1.01 to 5.48. The toxicities of ILs to Q67 mainly depended on the alkyl chain length and every two-carbon augment on the alkyl chain made the toxicity duplicate. The anions, cation skeletons and light absorbance of ILs showed no significant effect on the toxicities of ILs to Q67.

A novel direct equipartition ray design (EquRay) procedure for toxicity interaction between ionic liquid and dichlorvos.

BACKGROUND, AIM AND SCOPE: Pollutants always co-exist in the environment. Determining and characterizing the interaction among chemicals is an important issue. Experimental designs (ED) play an important role in evaluating the interactions. The main aim of our study is to provide the test and analysis of the toxicity interaction with a novel ED method. MATERIALS AND METHODS: A novel direct equipartition ray design (EquRay) procedure was proposed to effectively and systematically determine the toxicities of binary mixtures on Vibrio qinghaiensis sp.-Q67. Here, one component is ionic liquid, 1-butyl-2,3-dimethylimidazolium chloride (IL1), 1-butylpyridinium bromide (IL2) or N-hexylpyridinium bis(trifluoromethylsulfonyl)imide (IL3), and another is dichlorvos (DIC). The toxicity interaction was evaluated by comparing experiment and additive model together with three-dimension deviation response surface (DRS) analysis. RESULT: Selecting CA as a reference model, the binary mixtures exerted less than additive (antagonism). Most of the deviations occurred in the centre portion of the DRS where the dCA (deviation from CA) values are between -15% and -26% for IL1-DIC and IL2-DIC mixtures and -10% and -15% for IL3 and DIC. Selecting IA as a additive model, IL1-DIC and IL2-DIC mixtures exhibited less than additive (antagonism) while IL3-DIC displayed an addition action and the absolute values of dIAs (deviation from IA) were less than 10%. CONCLUSION: A novel EquRay procedure was developed in this study and the EquRay can provide us with the information about the toxicity interaction between binary mixture components (such as DIC and IL) in different concentration regions across different mixture ratios.

Evaluation on the toxicity of ionic liquid mixture with antagonism and synergism to Vibrio qinghaiensis sp.-Q67.

Ionic liquids (ILs) are a fascinating group of new chemicals with the potential to replace the classical volatile organic solvents, stimulating many applications in chemical industry. In case ILs are released to the environment, possible combined toxicity should be taken into account and it is, however, often neglected up to now. In this paper, therefore, the concentration-response curves (CRCs) of four groups of IL mixtures with various mixture ratios to Vibrio qinghaiensis sp.-Q67 were determined using the microplate toxicity analysis and were compared to the CRCs predicted by an additive reference model, the concentration addition (CA) or independent action (IA), to identify the toxicity interaction. It is showed that most of the IL mixture rays displayed the classical addition while the remaining rays exhibited antagonism or synergism. Moreover, it is found that the pEC50 values of the mixture rays exhibiting antagonism or synergism are well correlated with the mixture ratio of a certain IL therein.