Accelerated mineralization of textile wastewater under 222 nm irradiation from Kr/Cl2 excilamp: an environmentally friendly and energy efficient approach.

The textile dyeing and manufacturing industry is the major producer of significant amounts of wastewater that contain persistent substances such as azo dyes that require adequate remediation measures. Far ultraviolet at 222 nm light may provide an advantage for contaminants degradation as compared to conventional UV sources (254 nm). In this paper, the degradation of reactive black 5 (RB5) in artificial wastewater has been performed using a 222 nm Kr/Cl2 excimer source under direct photolysis and an advanced oxidation process using TiO2/H2O2. The solution pH, catalyst concentration, 222 nm intensity, initial concentration of dye, and addition of H2O2 influence the degradation rate constant. The molar absorption coefficient, quantum yield of RB5 at 222 nm and the electrical energy per order (EEO) from different treatment methods have been reported. RB5 shows 1.26 times higher molar absorption at 222 nm than at 254 nm. The EEO for excimer-222/H2O2 ( ∼ 13 kWh/m3) is five times lower than that of the excimer-222/TiO2 process, which makes the process energy efficient. The degradation of wastewater has been carried out at three distinct pH values (2, 6, and 10), and the pH level of 10 exhibited the highest degree of degradation. The degradation rate in the alkaline medium is 8.27 and 2.05 times higher than in the acidic or ambient medium. Since textile effluent is highly alkaline, this result is significant, as no neutralization of the wastewater is required, and direct treatment is possible. A possible degradation pathway has been established based on Fourier transform infrared spectroscopy (FTIR) and high resolution mass spectroscopy (HRMS) analysis. The phytotoxicity of the treated wastewater has also been evaluated for its suitability for reuse in agriculture. The study reveals that the excimer-222/H2O2 treated wastewater significantly enhanced the germination percentage of Raphanus sativus seed (97%) compared to dye wastewater-grown seeds (75%). This work offers crucial information for future studies on the direct and indirect photolysis of azo dyes, as well as insight into the process of RB5 degradation under Kr/Cl2 excimer radiation.

Application of Fe0.66Cu0.33@Al(OH)3 catalyst from fluidized-bed crystallizer by-product for RB5 azo dye treatment using visible light-assisted photo-Fenton technology.

This study aims to explore the reusability of wastewater treatment by-product for photo-Fenton process to treat an organic pollutant model. The optimal condition, reactive oxygen species (ROS), and kinetic approach in photo-Fenton process was discussed. The Metal oxide crystal pellets from are a by-product of the Fluidized-Bed Crystallization (FBC) process and can be used as a catalyst in the Photo-Fenton process. Electroplating wastewater containing iron and copper was treated via the FBC process using granulated Al(OH)3 as carrier seeds. The binary oxide of FeOOH and Cu2O on the Al(OH)3 surface (Fe0.66Cu0.33@Al(OH)3) was identified as the FBC by-product after characterization using FTIR and XPS analysis. In the photo-Fenton process, visible light from a fluorescence lamp with a wavelength of 400-610 nm was chosen as an irradiation source. Oxalic acid was added as chelating agent to form photosensitive iron oxalate species and hydrogen peroxide was applied as oxidant to generate active radical to decolorize and mineralize RB5 synthesized solution (100 mg/L). The operating conditions including the oxalic acid to pollutant ratio ([OA]0/[RB5]0) of 4.5-13.0, reaction pH (pHr) of 3-7 and initial to theoretical hydrogen peroxide molar ratio [H2O2]0/[ H2O2]theoretical of 35%-120% were optimized. Under the optimal conditions, pHr = 5.0; [H2O2]0/[RB5]0 at 75% stoichiometric and [OA]0/[RB5]0 = 9, the RB5 is almost completely decolorized after 210 min of operation and the mineralization efficiency is 58%. The contribution of •OH, O2•-, and O21 to the Photo-Fenton system was determined using ESR analysis with the addition of DMPO and TEMP as spin trap agents. The kinetic analysis reveals the observed rate constants kRB5, kOA and kR from fitting are 0.0120, 0.0054 and 0.0001 M-1s-1, respectively.

Method to determine the decolorization potential of persistent dyes by white rot fungi by colorimetric assays.

Decolorization assays allow to assess the ability of white rot fungi to degrade persistent organic molecules such as textile dyes and can contribute to discover microorganisms that can be used for bioremediation. The decolorization can be overlayed by the absorption from metabolites that are produced by fungi during screening, which interfere with the results. To compensate for this interference a method was developed by using different controls to subtract interfering signals. The method was designed for simple screening in multiwell plates that can be operated with a plate reader. It was applied to four different textile dyes (Reactive Black 5, Reactive Blue 4, Reactive Green 19, and Reactive Orange 16) that were degraded by the white rot fungus Phanerochaete velutina. The four textile dyes showed different results with a different degree of interference. The controls allow to compensate for interfering signals and to calculate kinetic parameters for the decolorization reaction and the enzymatic degradation.•Determine the non-enzymatic degradation of the dyes in experiments without fungi.•Determine the absorbance of metabolites and subtract it from the decolorization data to obtain the degradation of the dye.•Determine kinetic parameters of the degradation to compare the efficiency of the enzymes towards dyes.

Optimization of the Decolorization of the Reactive Black 5 by a Laccase-like Active Cell-Free Supernatant from Coriolopsis gallica.

The textile industry generates huge volumes of colored wastewater that require multiple treatments to remove persistent toxic and carcinogenic dyes. Here we studied the decolorization of a recalcitrant azo dye, Reactive Black 5, using laccase-like active cell-free supernatant from Coriolopsis gallica. Decolorization was optimized in a 1 mL reaction mixture using the response surface methodology (RSM) to test the influence of five variables, i.e., laccase-like activity, dye concentration, redox mediator (HBT) concentration, pH, and temperature, on dye decolorization. Statistical tests were used to determine regression coefficients and the quality of the models used, as well as significant factors and/or factor interactions. Maximum decolorization was achieved at 120 min (82 ± 0.6%) with the optimized protocol, i.e., laccase-like activity at 0.5 U mL−1, dye at 25 mg L−1, HBT at 4.5 mM, pH at 4.2 and temperature at 55 °C. The model proved significant (ANOVA test with p < 0.001): coefficient of determination (R²) was 89.78%, adjusted coefficient of determination (R²A) was 87.85%, and root mean square error (RMSE) was 10.48%. The reaction conditions yielding maximum decolorization were tested in a larger volume of 500 mL reaction mixture. Under these conditions, the decolorization rate reached 77.6 ± 0.4%, which was in good agreement with the value found on the 1 mL scale. RB5 decolorization was further evaluated using the UV-visible spectra of the treated and untreated dyes.

Photodegradation assessment of RB5 dye by utilizing WO3/TiO2 nanocomposite: a cytotoxicity study.

Textile dyeing wastewater becomes one of the root causes of environmental pollution. Titanium dioxide (TiO2) is one of the photocatalysts that shows prominent organic dye photodegradation ability. In this study, a porous tungsten oxide (WO3)/TiO2 composite was prepared through ultrasonic-assisted solvothermal technique with varying amounts of WO3 ranging from 0.25 to 5 weight % (wt.%). The prepared 0.50 wt.% WO3/TiO2 (0.50WTi) composite exhibited the highest photodegradation activity (4.39 × 10-2 min-1) and complete mineralization in chemical oxygen demand (COD) reading towards 30 mg.L-1 of Reactive Black 5 (RB5) dye under 60 min of light irradiation. Effects of large surface area, small crystallite size, high pore volume and size, and low electron-hole pair recombination rate attributed to the superiority of 0.50WTi. Besides, 0.50WTi could be reused, showing 86.50% of RB5 photodegradation at the fifth cycle. Scavenger study demonstrated that photogenerated hole (h+) was the main active species of 0.50WTi to initiate the RB5 photodegradation. Cytotoxicity assessment determined the readings of half-maximal inhibitory concentration (IC50) were 1 mg.mL-1 and 0.61 mg.mL-1 (24 and 72 h of incubations) for the 0.50WTi composite.

Development of a semiconductor tree branch-like photoreactor for textile industry effluent treatment.

This paper aimed to develop a new photocatalytic reactor design with a rotary tree branch structure for wastewater treatment in the textile industry. The brass sheet calcined at 500 °C (B500) was used as the photocatalyst and as a substrate for ZnO nanoparticle immobilization (B500ZnO). The photoreactor performance was evaluated toward the photodegradation of an aqueous solution of Reactive Black 5 dye (AS-RB5), raw wastewater (RW), and treated wastewater (TW). X-ray diffraction (XRD) and scanning electron microscopy (SEM) results illustrated ZnO nanowire formation over B500 and B500ZnO substrates. The bandgap values of these samples were estimated by diffuse reflectance measurements. The effects of dye concentration, the type of radiation, and ZnO NP deposition on the degradation of AS-RB were evaluated. Decreases in chemical oxygen demand (COD) greater than 82% were obtained using solar irradiation and artificial light as the energy source. Regarding calcined brass sheet reutilization, a decrease of 45% in the photocatalytic activity efficiency after 5 cycles was noted due to the effect of photocorrosion of the ZnO nanowires. The photoreaction of the RW and TW effluents showed COD values of 21 and 35%, respectively, which are below the limits established by state environmental control. With respect to RB5 addition to the TW effluent (TW-RB5), a discoloration of 62% was noticed after 3 h of photodegradation. Furthermore, the toxicity tests of the AS-RB5 and TW-RB5 samples did not display toxic intermediates after the photoreaction since 80% of the seeds germinated. Finally, the photoreactor exhibited good performance regarding the decrease in effluent pollutant charge, in addition to the efficient discoloration of RB5 dye.

Site directed confinement of laccases in a porous scaffold towards robustness and selectivity.

We immobilized a fungal laccase with only two spatially close lysines available for functionalization into macrocellular Si(HIPE) monoliths for the purpose of continuous flow catalysis. Immobilization (30-45 % protein immobilization yields) was obtained using a covalent bond forming reaction between the enzyme and low glutaraldehyde (0.625 % (w/w)) functionalized foams. Testing primarily HBT-mediated RB5 dye decolorization in continuous flow reactors, we show that the activity of the heterogeneous catalyst is comparable to its homogeneous counterpart. More, its operational activity remains as high as 60 % after twelve consecutive decolorization cycles as well as after one-year storage, performances remarkable for such a material. We further immobilized two variants of the laccase containing a unique lysine: one located in the vicinity of the substrate oxidation site (K157) and one at the opposite side of this oxidation site (K71) to study the effect of the proximity of the Si(HIPE) surface on enzyme activity. Comparing activities on different substrates for monoliths with differentially oriented catalysts, we show a twofold discrimination for ABTS relative to ascorbate. This study provides ground for the development of neo-functionalized materials that beyond allowing stability and reusability will become synergic partners in the catalytic process.

Synthesis and Characterization of Fe-TiO2 Nanomaterial: Performance Evaluation for RB5 Decolorization and In Vitro Antibacterial Studies.

A photocatalytic system for decolorization of double azo reactive black 5 (RB5) dye and water disinfection of E. coli was developed. Sol gel method was employed for the synthesis of Fe-TiO2 photocatalysts and were characterized using thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS) and Brunauer-Emmett-Teller (BET) analysis. Results showed that photocatalytic efficiency was greatly influenced by 0.1 weight percent iron loading and 300 °C calcination temperature. The optimized reaction parameters were found to be the ambient temperature, working solution pH 6.2 and 1 mg g-1 dose to completely decolorize RB5. The isotherm studies showed that RB5 adsorption by Fe-TiO2 followed the Langmuir isotherm with maximum adsorption capacity of 42.7 mg g-1 and Kads 0.0079 L mg-1. Under illumination, the modified photocatalytic material had higher decolorization efficiency as compared to unmodified photocatalyst. Kinetic studies of the modified material under visible light irradiation indicated the reaction followed the pseudo-first-order kinetics. The illumination reaction followed the Langmuir-Hinshelwood (L-H) model as the rate of dye decolorization increased with an incremental increase in dye concentration. The L-H constant Kc was 1.5542 mg L-1∙h-1 while Kads was found 0.1317 L mg-1. The best photocatalyst showed prominent percent reduction of E. coli in 120 min. Finally, 0.1Fe-TiO2-300 could be an efficient photocatalyst and can provide a composite solution for RB5 decolorization and bacterial strain inhibition.

Purification, characterization and cytotoxic properties of a bacterial RNase.

An RNase produced by Bacillus safensis RB-5 was purified up to 22.32-fold by successive techniques of salting out, DEAE-anion exchange and gel permeation (Sephadex G-100) chromatography techniques with a yield of 2.27%. The purified RNase possessed a single band in SDS-PAGE (Mr ~ 60 kDa). The purified RNase showed optimal activity at temperature of 37 °C and pH 7.5 in the presence of substrate (Yeast RNA) and Mg2+ ions. The RNase activity was strongly inhibited by Hg2+ and mildly by Fe2+, Ba2+ and Zn2+ ions. Its half-life was found to be 8 h at 37 °C. The RNase kinetics study showed Km and Vmax value of 0.3 mM and 9.2 µmol/mg/min, respectively. The purified RNase also showed cytotoxic and antiproliferative activities towards a few transformed cell lines. The purified RNase (IC50 0.035 U/mL) effectively inhibited RD and Hep-2C cells proliferation & migration, while sparing HEK 293 cells. The purified RNase was cytotoxic as well as effective degrader of the RNA of transformed RD cells at low concentration. Moreover, the purified RNase of B. safensis RB-5 was found to possess a little hemolytic activity towards human RBCs.

Five-factor-at-a-time (FFAT) approach for optimal production of an extracellular RNase from Bacillus safensis RB-5.

A Gram-positive, rod-shaped, endospore-forming, and RNA-degrading bacterium RB-5 was isolated from a soil sample. Based on 16-rDNA gene sequence, the bacterium RB-5 was identified as Bacillus safensis (Accession number KX443714.1). The bacterium appeared to be related to Bacillus safensis KL-052, an other-member of genus Bacillus. One-factor-at-a-time (OFAT) and Response Surface Methodology (RSM) statistical approaches were used to optimize the fermentation broth to obtain an improved extracellular RNase production from B. safensis RB-5. These approaches improved RNase activity of B. safensis KL-052 from 4.26 to 7.85 U/mL. The OFAT approach was used to study the effects of supplementation of carbon, nitrogen and physical conditions, which included temperature, pH and agitation rate on extracellular RNase production by B. safensis KL-052. Five variables screened by Central Composite Design (CCD) were employed to evaluate their interactive effects on RNase production by the organism. CCD selected 25 factorial values obtained by the statistical approach were peptone 1.13% (w/v), sodium nitrate 1.13% (w/v), MgSO4 0.06% (w/v), pH 8.5, and temperature 35 °C for RNase production by B. safensis. The highest predicted value of RNase was 7.05 U/ml while actual obtained value was 7.85 U/ml that was ∼84% and 1.84-fold higher than OFAT approach.

Comparative study of antiestrogenic activity of two dyes after Fenton oxidation and biological degradation.

In present study, two methods (Fenton oxidation and biological degradation) were used to degrade azo dye (Reactive Black 5, RB5) and anthraquinone dye (Remazol Brilliant Blue R, RBBR). The changes of antiestrogenic activities of these two dyes through two degradation methods were detected using the yeast two-hybrid assay method. Fluorescence spectroscopy together with gas chromatography-mass spectrometry (GC-MS) method was performed to analyze the metabolites of RB5 and RBBR after Fenton oxidation and biological degradation. Results indicated that by Fenton oxidation, the decolorization of RB5 and RBBR were 99.31% and 96.62%, respectively, which were much higher than that by biological degradation. Dissolved organic carbon (DOC) reduction rates of RB5 and RBBR after Fenton oxidation were also much higher than that after biological degradation. By Fenton oxidation, the antiestrogenic activities of RB5 and RBBR all decreased below detection limit after degradation, while by biological degradation all of them increased significantly after degradation. Fluorescence spectroscopy analysis and GC-MS analysis confirmed the degradation effects of RB5 and RBBR by these two degradation methods. In addition, fluorescence spectroscopy analysis revealed that the metabolites humic acid-like substances might contribute to the increasing of antiestrogenic activity of RB5 and RBBR after biological degradation.

Decolorization of Reactive Black 5 Dye by Heterogeneous Photocatalysis with TiO 2 /UV / Decoloración del tinte Negro Remazol B mediante fotocatálisis heterogénea con TiO 2 /UV / Descoloração do corante sintético Negro Remazol B por fotocatálise heterogênea com TiO 2 /UV

Abstract Reactive Black 5 (RB5) is an azo dye widely used in the textile industry because of its high chemical stability. Since it does not entirely fix on the fabrics, it pollutes water sources. In this work, the decolorization of aqueous solutions with RB5 was performed by heterogeneous photocatalysis with TiO2/UV. The reaction was carried out in an aluminum photoreactor equipped with five lamps. The effect of TiO2 (0.1, 0.175, and 0.25 g L-1), RB5 concentration (50, 75, and 100 mg L-1), and pH (3, 7, and 11) was evaluated for 14 h, using a Box-Behnken experimental statistical design. Complete decolorization of RB5 was obtained at 14 h, employing 0.175 g L-1 TiO2, 50 mg L-1 RB5, and pH 3. A 98.44% of decolorization was achieved in 10 h (0.25 g L-1 of TiO2, 50 mg L-1 of RB5, and pH 7). The highest decolorization percentage of RB5 (99.51%) was obtained at 10 h of exposure to UV light, using 0.5 g L-1 of TiO2, 50 mg L-1 of the dye, and a pH of 3. Cytotoxicity tests on the HepG2 cell line indicated that photocatalytic degradation of RB5 did not generate cytotoxic byproducts.

Resumen El Negro Remazol B (NRB) es un colorante azoico, usado en la industria textil por su estabilidad química. Este tinte no se fija al 100%, ocasionando contaminación en el agua. En este trabajo se evaluó la decoloración de soluciones acuosas con NRB mediante fotocatálisis heterogénea con TiO2/UV. La reacción se realizó en un fotorreactor de aluminio equipado con cinco lámparas. El efecto de la concentración de TiO2 (0,1; 0,175 y 0,25 g L-1), y NRB (50, 75 y 100 mg L-1) y el pH (3, 7 y 11) fue evaluado durante 14 h, tomando un diseño estadístico experimental Box-Behnken. La decoloración completa del NRB se obtuvo después de 14 h (0,175 g L-1 de TiO2, 50 mg L-1 de NRB, y pH 3). Se alcanzó un 98,44% de decoloración después de 10 h (0,25 g L-1 de TiO2, 50 mg L-1 de NRB, y pH 7). Se encontró que el mejor porcentaje de decoloración del NRB (99,51%) se obtuvo a las 10 h de exposición a luz UV, utilizando 0,5 g L-1 de TiO2, 50 mg L-1 del colorante y un pH de 3. Los ensayos de citotoxicidad sobre la línea celular HepG2 indicaron que la degradación fotocatalítica del NRB no generó subproductos citotóxicos.

Resumo O Negro Remazol B (RNB) é um corante azoico usado na indústria têxtil pela sua estabilidade química. O corante não é fixo no tecido em 100%, então contamina as fontes de água. Neste trabalho, avaliou-se a descoloração de soluções aquosas com RNB por meio de fotocatálise heterogênea com TiO2/UV. A reação foi feita no fotoreactor de alumínio com cinco lâmpadas. O efeito da concentração de TiO2 (0,1; 0,175 e 0,25 g L-1), RNB (50, 75 e 100 mg L-1) e pH (3, 7 e 11) foi avaliado durante 14 h utilizando o modelo estatístico Box-Behnken. Ás 14 h, foi atingida a descoloração completa do RNB (pH 3; 0,175 g L-1 de TiO2 e 50 mg L-1 de RNB). Utilizando 0,25 g L-1 de TiO2, 50 mg L-1 de RNB e pH 7, obteve-se descoloração de 98,44% em 10 h. Encontrou-se que a melhor porcentagem de descoloração do RNB (91,51%) foi obtida com 10 h de exposição à luz UV usando 0,5 g L-1 de TiO2, 50 mg L-1 do corante e pH de 3. Adicionalmente, os testes de citotoxicidade na linha celular HepG2 mostraram que a degradação fotocatalítica do RNB não gerou subprodutos citotóxicos.

Combined strategy for removal of Reactive Black 5 by biomass sorption on Macrocystis pyrifera and zerovalent iron nanoparticles.

Reactive Black 5, RB5, has been used as a model azo dye to evaluate the removal efficiency of sorption on Macrocystis pyrifera biomass (Mpyr) and commercial zerovalent iron nanoparticles (nZVI) in individual and combined treatments. The best conditions for the treatment with the isolated materials were first determined, and then, in series and combined treatments were performed under these conditions, achieving removal efficiencies higher than 80% of the initial dye concentration. Strengths and weaknesses of all removal strategies (individual, in series and combined) are analyzed regarding the application on real effluents. Mpyr efficiently adsorbed RB5, but also increased the total organic content by partial dissolution of components of the algal biomass. Removal experiments with commercial nZVI were also efficient but liberated Fe to the solution, and sulfanilic acid was observed after the treatment as a product of RB5 degradation. In contrast, after the Mpyr treatment, no sulfanilic acid was detected, suggesting that sulfanilic acid is efficiently adsorbed by the biomass. The best condition was the integrated use of Mpyr and nZVI, with a remarkable removal efficiency (69-80%) obtained after only 1 h of treatment. Finally, nZVI were successfully immobilized in Mpyr, and the hybrid material was used to remove RB5 in continuous flow experiments at pH 3, obtaining a removal capacity of 39.9 mg RB5 g-1 after a total processed volume of 630 mL of [RB5]0 = 100 mg L-1.

A valuable peroxidase activity from the novel species Nonomuraea gerenzanensis growing on alkali lignin.

Degradation of lignin constitutes a key step in processing biomass to become useful monomers but it remains challenging. Compared to fungi, bacteria are much less characterized with respect to their lignin metabolism, although it is reported that many soil bacteria, especially actinomycetes, attack and solubilize lignin. In this work, we screened 43 filamentous actinomycetes by assaying their activity on chemically different substrates including a soluble and semi-degraded lignin derivative (known as alkali lignin or Kraft lignin), and we discovered a novel and valuable peroxidase activity produced by the recently classified actinomycete Nonomuraea gerenzanensis. Compared to known fungal manganese and versatile peroxidases, the stability of N. gerenzanensis peroxidase activity at alkaline pHs and its thermostability are significantly higher. From a kinetic point of view, N. gerenzanensis peroxidase activity shows a Km for H2O2 similar to that of Phanerochaete chrysosporium and Bjerkandera enzymes and a lower affinity for Mn2+, whereas it differs from the six Pleurotus ostreatus manganese peroxidase isoenzymes described in the literature. Additionally, N. gerenzanensis peroxidase shows a remarkable dye-decolorizing activity that expands its substrate range and paves the way for an industrial use of this enzyme. These results confirm that by exploring new bacterial diversity, we may be able to discover and exploit alternative biological tools putatively involved in lignin modification and degradation.

Two new triterpenoid saponins from ginseng medicinal fungal substance.

Two new dammarane-type triterpenoid saponins, namely ginsenosides Rb4 (1) and Rb5 (2), were isolated from ginseng medicinal fungal substance. The structures of 1 and 2 were established as 3ß,12ß,20(S)-trihydroxydammar-24(25)-ene-3-O-[α-d-glucopyranosyl-(1→4)-ß-d-glucopyranosyl-(1→2)-ß-d-glucopyranosyl]-20-O-ß-d-glucopyranoside and 3ß,12ß,20(S)-trihydroxydammar-24(25)-ene-3-O-[α-d-glucopyranosyl-(1→4)-α-d-glucopyranosyl-(1→4)-ß-d-glucopyranosyl-(1→2)-ß-d-glucopyranosyl]-20-O-ß-d-glucopyranoside on the basis of spectroscopic analysis and chemical analysis, respectively.