Preparation of novel Fe-containing zeolite-A for KN-R decolorization by Fenton-like reaction.

Herein, novel catalysts of Fe-containing zeolite-A (Fe/zeolite-A) were synthesized by exchanging iron ions into zeolite-A framework, and short-chain organic acids (SCOAs) were employed as chelating agents. Reactive Brilliant Blue KN-R (KN-R) was used as a model pollutant to evaluate the performance of these catalysts based on the heterogeneous Fenton reaction. The results showed that Fe-OA/3A, which applied zeolite-3A as the supporter and oxalic as the chelating agent, presented the most prominent KN-R decolorization efficiency. Under the initial pH of 2.5, 0.4 mM KN-R could be totally decolorized within 20 min. However, the mineralization efficiency of KN-R was only 58.2%. Therefore, anthraquinone dyes were introduced to modify zeolite-3A. As a result, the mineralization efficiency of KN-R was elevated to 92.7% when using Alizarin Violet (AV) as the modifier. Moreover, the modified catalysts exhibited excellent stability, the KN-R decolorization efficiency could be maintained above 95.0% within 20 min after operating for nine cycles. The mechanism revealed that the Fe(II)/Fe(III) cycle was accelerated by AV-modified catalyst thus prompting the KN-R decolorization in Fenton-like system. These findings provide new insights for preparing catalysts with excellent activity and stability for dye wastewater treatment.

Hydrogen bond-mediated self-assembly of Tin (II) oxide wrapped with Chitosan/[BzPy]Cl network: An effective bionanocomposite for textile wastewater remediation.

A novel and efficient bionanocomposite was synthesized by incorporating SnO into chitosan (Ch) and a room-temperature ionic liquid (RTIL). The bionanocomposite was synthesized in benzoyl pyridinium chloride [BzPy]Cl to maintain the unique properties of SnO, chitosan, and the ionic liquid. Adsorption and photodegradation processes were applied to evaluate the bionanocomposite for removing azo and anthraquinone dyes and textile wastewater. SnO/[BzPy]Cl and SnO/[BzPy]Cl/Ch samples were prepared and characterized using various techniques, including FT-IR, SEM, XRD, EDAX, XPS, DSC, TGA, nitrogen adsorption/desorption isotherm, and DRS analysis. SEM analysis revealed a hierarchical roughened rose flower-like morphology for the biocomposite. The band gap energies of SnO/[BzPy]Cl and SnO/[BzPy]Cl/chitosan were found to be 3.9 and 3.3 eV, respectively, indicating a reduction in the band gap energy with the introduction of [BzPy]Cl and chitosan. SnO/[BzPy]Cl/Ch showed high removal rates (92-95 %) for Fast Red, Blue 15, Red 120, Blue 94, Yellow 160, and Acid Orange 7 dyes. The adsorption kinetics followed a pseudo-second-order model. In addition, the effect of different photodegradation parameters such as solution pH, dye concentrations, contact time, and amount of photocatalyst, was studied. Given the optimal results obtained in removing azo and anthraquinone dyes, the SnO/[BzPy]Cl/Ch nanocomposite was used as an efficient nanocomposite for removing dyes from textile wastewater. The highest removal efficiency was found to be 95.8 %, obtained under ultraviolet and visible light. Furthermore, BOD and COD reduction analysis showed significant reductions, indicating the excellent performance of the photocatalyst.

Mycoremediation of anthraquinone dyes from textile industries: a mini-review.

The discharge of wastewater from textile industries into aquatic bodies has severe health and environmental impacts. Textile industries generate huge amounts of effluents containing hazardous toxic dyes. Anthraquinone (AQ) dyes containing AQ chromophore groups are the second most important class of nondegradable textile dyes, preceded by azo dyes. Despite their prevalence, biodegradation of AQ dyes has not yet been completely understood because of their complex and stable structures. Currently, microbiological approaches to treating dyeing wastewater are considered economical and feasible, and reports regarding fungal degradation of AQ dyes are increasing. Structures and classification of AQ dyes were summarized in this study along with degradative fungi, and their enzyme systems with influencing factors and possible mechanisms of AQ mycoremediation were explored. Furthermore, the existing problems and present research progress were discussed. Finally, the key points with future research directions were presented.

SERS detection of anthraquinone dyes: Using solvothermal silver colloid as the substrate.

Anthraquinone dyes have been widely used to color textile fibers since antiquity. Identification of the dyes can help us understand the dyeing processes and when and where the textiles were produced. Herein, we present a strategy based on surface-enhanced Raman scattering (SERS) with a novel silver colloid substrate for the detection of anthraquinone dyes. Quasi-spherical silver particles with different sizes were prepared by the solvothermal method and then characterized by transmission electron microscopy (TEM). The silver colloid substrates exhibited high-density hot spots with good reproducibility (RSDs of 3 âˆ¼ 16 %) and high sensitivity. Among them, Ag-C2 (the molar ratio of AgNO3 to PVP is 0.367, reacted for 2 h) was used to detect anthraquinone dyes in reference silk fibers as well as ancient textile samples due to the highest sensitivity and the low RSD (5.37 %) in this study. More importantly, Ag-C2 can be utilized to distinguish three madder species (Rubia tinctorum, Rubia cordifolia, and Rubia argyi) depending on the SERS intensity of alizarin and purpurin.

Transformation of Reactive Blue 19 by a recombinant peroxidase DyP.

Wastewater containing recalcitrant dyes causes environmental problems. A new superfamily of heme-containing peroxidases, dye-decolorizing peroxidases (DyPs), has been found to decolorize different kinds of dyes, especial anthraquinone dyes efficiently. However, the mechanism of dyes degradation by DyPs has not been fully understood and the toxicity of dye degradation intermediates by DyPs catalysis to microbes is unclear. In this study, a purified recombinant Thermobifida fusca DyP (TfuDyP) in E. coli BL21(DE3) was used to treat Reactive Blue 19 (RB19), an anthraquinone dye. The reaction intermediates analyzed by ultra performance liquid chromatography/mass spectroscopy (UPLC-MS) indicated the initial site of TfuDyP attack on RB19. In addition, it was found that both RB19 and its incomplete degradation products inhibited the growth of Bacillus subtilis. These findings provided a novel understanding of DyPs catalysis to anthraquinone dyes.

Review on effect of different type of dyes on advanced oxidation processes (AOPs) for textile color removal.

The textile industry is one of the most valuable industries, especially in developing countries, because it employs a large portion of the workforce. However, the development of the textile industry has led to increasing concern about environmental issues. Wastewater from the textile industry has a high COD and an undesirable color. Color is one of the problems with the wastewater due to its toxicity and low biodegradability. Color in textile wastewater mainly originates from the dyestuff used during the dyeing or printing process. Amongst all of available technology for color removal, advanced oxidation processes (AOPs) are considered one of the best and the most potential technology. However, the understanding of AOPs reaction mechanism to degrade dyestuff is still limited. In general, dyes degradation mechanism will vary and mainly depend on the chemical structure of the dyes itself. Some reaction pathway that seems less favorable thermodynamically can still happen during the process. Understanding the mechanism will be beneficial for future dyes improvement, especially on developing the moiety of the aromatic compound in order to produce easily degraded dyes while maintaining the fastness quality.

Catalytic and Physicochemical Evaluation of a TiO2/ZnO/Laccase Biocatalytic System: Application in the Decolorization of Azo and Anthraquinone Dyes.

A TiO2/ZnO oxide system was proposed as a support for the immobilization of laccase from Trametes versicolor (LTV). The obtained TiO2/ZnO/LTV biocatalytic system was then applied in the decolorization/degradation of C.I. Reactive Black 5 and C.I. Acid Green 25 dyes. The efficiency of immobilization was evaluated based on catalytic properties (Bradford method, oxidation reaction of 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)) and physicochemical (spectroscopic, porous, electrokinetic) analysis. The immobilization process was carried out with high performance (99.4%). Immobilized laccase retained about 40% of its activity in the whole analyzed temperature range and after 10 reaction cycles. Immobilization efficiency was also indirectly confirmed by the presence of characteristic functional groups (-C-H and -C-O), nitrogen and carbon on the TiO2/ZnO/LTV biocatalytic surface, identified by spectroscopic analyses. The increase in the surface area to 126 m2/g, change of isoelectric point (2.0) and zeta potential ranges (from +12.0 to -20.0 mV) after the immobilization process were also observed. The results show that the designed biocatalytic system enables the removal of acid dyes (C.I. Reactive Black 5 and C.I. Acid Green 25) with high efficiency (99% and 70%, respectively). Mass spectroscopy analysis indicated possible degradation products formed by the cleavage of N=N and C-N bonds.

Multifunctional 3D cationic starch/nanofibrillated cellulose/silver nanoparticles nanocomposite cryogel: Synthesis, adsorption, and antibacterial characteristics.

We report a new 3D nanocomposite cryogel combines the advantages of cationic starch (Cs), nanofibrillated cellulose (NFC) and silver nanoparticles (Ag NPs). Cs was the main component of the cryogel while NFC was used as a filling agent to enhance the mechanical properties of the produced cryogel. Both Cs and NFC endow the cryogel with adsorption properties while Ag NPs enhances its antibacterial properties. Ag NPs was green synthesized with the aid of microwave radiation using NFC as reducing and stabilizing agent. The prepared Ag particles were free of impurities with sizes <10 nm and good stability in solution. Two different concentrations of the prepared Ag NPs were added to a mixture of Cs and NFC and subjected to freeze drying to get porous cryogel (3D microstructure). The Ag NPs free cryogel has highly porosity smooth surface with large surface area. Adding Ag NPs decreased these features and increased the 3D roughness. Optimum adsorption of reactive blue 49 was observed after 30 min of contact with 1.5 g/L of the cryogel at pH 1. The adsorption kinetics and isotherm were best described by the pseudo-first-order and Freundlich equations, respectively. All prepared cryogels have notable antibacterial properties that were significantly improved by adding Ag NPs. Overall, the new 3D composite cryogel can efficiently remove dyes and bacteria from wastewater.

Enhanced Reactive Blue 4 Biodegradation Performance of Newly Isolated white rot fungus Antrodia P5 by the Synergistic Effect of Herbal Extraction Residue.

In this study, a white rot fungus Antrodia was newly isolated and named P5. Then its dye biodegradation ability was investigated. Our results showed that P5 could effectively degrade 1,000 mg/L Reactive Blue 4 (RB4) in 24 h with 95% decolorization under shaking conditions. It could tolerate a high dye concentration of 2,500 mg/L as well as 10% salt concentration and a wide range of pH values (4-9). Herbal extraction residues (HER) were screened as additional medium elements for P5 biodegradation. Following the addition of Fructus Gardeniae (FG) extraction residue, the biodegradation performance of P5 was significantly enhanced, achieving 92% decolorization in 12 h. Transcriptome analysis showed that the expression of multiple peroxidase genes was simultaneously increased: Lignin Peroxidase, Manganese Peroxidase, Laccase, and Dye Decolorization Peroxidase. The maximum increase in Lignin Peroxidase reached 10.22-fold in the presence of FG. The results of UV scanning and LC-HRMS showed that with the synergistic effect of FG, P5 could remarkably accelerate the biodegradation process of RB4 intermediates. Moreover, the fungal treatment with FG also promoted the abatement of RB4 toxicity. In sum, white rot fungus and herbal extraction residue were combined and used in the treatment of anthraquinone dye. This could be applied in practical contexts to realize an efficient and eco-friendly strategy for industrial dye wastewater treatment.

Morphological and Behavioral Effects in Zebrafish Embryos after Exposure to Smoke Dyes.

Solvent Violet 47 (SV47) and Disperse Blue 14 (DB14) are two anthraquinone dyes that were previously used in different formulations for the production of violet-colored smoke. Both dyes have shown potential for toxicity; however, there is no comprehensive understanding of their effects. Zebrafish embryos were exposed to SV47 or DB14 from 6 to 120 h post fertilization (hpf) to assess the dyes' potential adverse effects on developing embryos. The potential ability of both dyes to cross the blood-brain barrier was also assessed. At concentrations between 0.55 and 5.23 mg/L, SV47 showed a dose-dependent increase in mortality, jaw malformation, axis curvature, and edemas. At concentrations between 0.15 and 7.54 mg/L, DB14 did not have this same dose-dependence but had similar morphological outcomes at the highest doses. Nevertheless, while SV47 showed significant mortality from 4.20 mg/L, there was no significant mortality on embryos exposed to DB14. Regardless, decreased locomotor movement was observed at all concentrations of DB14, suggesting an adverse neurodevelopmental effect. Overall, our results showed that at similar concentrations, SV47 and DB14 caused different types of phenotypic effects in zebrafish embryos.

Biodegradation and metabolic pathway of anthraquinone dyes by Trametes hirsuta D7 immobilized in light expanded clay aggregate and cytotoxicity assessment.

Biodegradation and metabolic pathways of three anthraquinone dyes, Reactive Blue 4 (RB4), Remazol Brilliant Blue - R (RBBR), and Acid Blue 129 (AB129) by Trametes hirsuta D7 fungus immobilized in light expanded clay aggregate (LECA) were investigated. Morphological characteristics observed with scanning electron microscope (SEM) showed successful immobilization of the fungus in LECA. Based on UV absorbance measurement, immobilized T. hirsuta D7 effectively degraded 90%, 95%, and 96% of RB4, RBBR and AB129, respectively. Metabolites were identified with high-resolution mass spectrometry (HRMS) and degradation pathway of the dyes by T. hirsuta D7 was proposed. Toxicity assay on human dermal fibroblast (HDF) showed that anthraquinone dyes exhibits significant toxicity of 35%, 40%, and 34% reduction of cell viability by RB4, RBBR, and AB129, respectively. Fungal treatment resulted in an abatement of the toxicity and cell viability was increased up to 94%. The data clearly showed the effectiveness of immobilized T. hirsuta D7 in LECA on detoxification of anthraquinone dyes. This study provides potential and fundamental understanding of wastewater treatment using the newly isolated fungus T. hirsuta D7.

Bacterial degradation of anthraquinone dyes.

Anthraquinone dyes, which contain anthraquinone chromophore groups, are the second largest class of dyes after azo dyes and are used extensively in textile industries. The majority of these dyes are resistant to degradation because of their complex and stable structures; consequently, a large number of anthraquinone dyes find their way into the environment causing serious pollution. At present, the microbiological approach to treating printing and dyeing wastewater is considered to be an economical and feasible method, and reports regarding the bacterial degradation of anthraquinone dyes are increasing. This paper reviews the classification and structures of anthraquinone dyes, summarizes the types of degradative bacteria, and explores the possible mechanisms and influencing factors of bacterial anthraquinone dye degradation. Present research progress and existing problems are further discussed. Finally, future research directions and key points are presented.

Dyeing Method and Properties of a Novel Blue Azo-Anthraquinone Reactive Dye on Cotton.

A novel blue azo-anthraquinone reactive dye was evaluated in the dyeing of cotton by using a dip-pad-steam process. Dyeing method and properties were examined in detail and the results showed that the dyeing method consisting of dye concentration of 25 g/L, sodium carbonate of 12 g/L, dipping time of 3 min and steaming time of 30 min was the most effective when a conventional "one-dip-one-nip" process was used. The fixation of the dyes on cotton could reach up to 93.4%, the wash and rub fastness both reached grade 4 above, and the light fastness reached grade 4-5 above. Such colored cotton showed very close colorimetric properties.

Composites of Anthraquinone Dyes@HKUST-1 with Tunable Microstructuring: Experimental and Theoretical Interaction Studies.

The metal-organic framework (MOF) HKUST-1 was employed as an interaction matrix for fundamental loading studies of anthraquinone dyes. Chosen dyes were alizarin (A), alizarin S (AS), disperse blue 1 (B1), disperse blue 3 (B3), disperse blue 56 (B56) and purpurin (P). All materials were characterized by XRD, FTIR, TGA and SEM. Hence the interaction of dyes with the framework was characterized by theoretical-experimental differential analysis. One-pot loading strategy resulted in more efficient scavenging of dyes, and reached 100 % for B56 using 50 mg L-1 . SEM revealed important microstructural changes, the smaller crystals ranged 0.8-3 µm in size and almost all composite sizes were from this to higher values, reaching 70 µm, with varying shapes. Two composites were larger in size range (about 2500-1000 µm), and were shaped as rods, octahedrons and coffin lids. Indeed, the microstructure could be modulated depending on preparation conditions and type of loaded dye. For the higher loading series, N2 adsorption and XPS experiments were carried on to further evidence dye-MOF interactions. Ab initio prediction of structural properties for A@HKUST-1 and P@HKUST-1 were obtained by means of solid-state CRYSTAL14 code at the PBE0 level of theory. Computed findings evidenced two O→Cu coordinative bonds, one from O-ketone and the other from O-phenolate moiety as main interactions towards CuNET centers.

Bacterial degradation of anthraquinone dyes / 浙江大学学报（英文版）（B辑：生物医学和生物技术）

Anthraquinone dyes, which contain anthraquinone chromophore groups, are the second largest class of dyes after azo dyes and are used extensively in textile industries. The majority of these dyes are resistant to degradation because of their complex and stable structures; consequently, a large number of anthraquinone dyes find their way into the environment causing serious pollution. At present, the microbiological approach to treating printing and dyeing wastewater is considered to be an economical and feasible method, and reports regarding the bacterial degradation of anthraquinone dyes are increasing. This paper reviews the classification and structures of anthraquinone dyes, summarizes the types of degradative bacteria, and explores the possible mechanisms and influencing factors of bacterial anthraquinone dye degradation. Present research progress and existing problems are further discussed. Finally, future research directions and key points are presented.

Bacterial degradation of anthraquinone dyes / 浙江大学学报（英文版）（B辑：生物医学和生物技术）

Anthraquinone dyes, which contain anthraquinone chromophore groups, are the second largest class of dyes after azo dyes and are used extensively in textile industries. The majority of these dyes are resistant to degradation because of their complex and stable structures; consequently, a large number of anthraquinone dyes find their way into the environment causing serious pollution. At present, the microbiological approach to treating printing and dyeing wastewater is considered to be an economical and feasible method, and reports regarding the bacterial degradation of anthraquinone dyes are increasing. This paper reviews the classification and structures of anthraquinone dyes, summarizes the types of degradative bacteria, and explores the possible mechanisms and influencing factors of bacterial anthraquinone dye degradation. Present research progress and existing problems are further discussed. Finally, future research directions and key points are presented.

Decolorization of Reactive Black 5 and Reactive Blue 4 Dyes in Microbial Fuel Cells.

Microbial fuel cells (MFCs) have potential to treat industrial wastewater containing organic compounds and simultaneously generate power. Organic compounds include textile dyes with various chromophore groups, which can be decolorized reductively by microorganisms under anaerobic conditions. In the present study, we examined the decolorization of Reactive Black 5 (RB5) azo dye and Reactive Blue 4 (RBL4) anthraquinone dye under open circuit potential in MFCs with graphite plate and graphite felt electrodes and a microbial consortium originally derived from bovine rumen fluid. RB5 dye was more than 90% decolorized in 120, 165, and 225 min at 50, 100, and 200 mg L-1 concentrations, respectively. RBL4 dye at 50 and 100 mg L-1 took 225 and 300 min to decolorize, while 200 mg L-1 RBL4 dye was not decolorized at all. Under closed circuit conditions, decolorization increased with decrease in external load, whereas current generation increased with external resistance. The results demonstrate that the reductive cleavage of the chromophore was more rapid with RB5 than with RBL4.

Identification, heterologous expression and characterization of a dye-decolorizing peroxidase of Pleurotus sapidus.

The coding sequence of a peroxidase from the secretome of Pleurotus sapidus was cloned from a cDNA library. Bioinformatic analyses revealed an open reading frame of 1551 bp corresponding to a primary translation product of 516 amino acids. The DyP-type peroxidase was heterologously produced in Trichoderma reesei with an activity of 55,000 U L-1. The enzyme was purified from the culture supernatant, biochemically characterized and the kinetic parameters were determined. The enzyme has an N-terminal signal peptide composed of 62 amino acids. Analysis by Blue Native PAGE and activity staining with ABTS, as well as gel filtration chromatography showed the native dimeric state of the enzyme (115 kDa). Analysis of the substrate range revealed that the recombinant enzyme catalyzes, in addition to the conversion of some classic peroxidase substrates such as 2,2'-azino-bis(3-ethylthiazoline-6-sulfonate) and substituted phenols like 2,6-dimethoxyphenol, also the decolorization of the anthraquinonic dye Reactive Blue 5. The enzyme also catalyzes bleaching of natural colorants such as ß-carotene and annatto. Surprisingly, ß-carotene was transformed in the presence and absence of H2O2 by rPsaDyP, however enzyme activity was increased by the addition of H2O2. This indicates that the rPsaDyP has an oxidase function in addition to a peroxidase activity. As a consequence of the high affinity to the characteristic substrate Reactive Blue 5 the rPsaDyP belongs functionally to the dyp-type peroxidase family.

Decolorization pathways of anthraquinone dye Disperse Blue 2BLN by Aspergillus sp. XJ-2 CGMCC12963.

Anthraquinone dye represents an important group of recalcitrant pollutants in dye wastewater. Aspergillus sp XJ-2 CGMCC12963 showed broad-spectrum decolorization ability, which could efficiently decolorize and degrade various anthraquinone dyes (50 mg L-1) under microaerophilic condition. And the decolorization rate of 93.3% was achieved at 120 h with Disperse Blue 2BLN (the target dye). Intermediates of degradation were detected by FTIR and GC-MS, which revealed the cleavage of anthraquinone chromophoric group and partial mineralization of target dye. In addition, extracellular manganese peroxidase showed the most closely related to the increasing of decolorization rate and biomass among intracellular and extracellular ligninolytic enzymes. Given these results, 2 possible degraded pathways of target dye by Aspergillus sp XJ-2 CGMCC12963 were proposed first in this work. The degradation of Disperse Blue 2BLN and broad spectrum decolorization ability provided the potential for Aspergillus sp XJ-2 CGMCC12963 in the treatment of wastewater containing anthraquinone dyes.