International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN IN 0976 INTERNATIONAL JOURNAL OF ADVANCED RESEARCH 6480(Print),

, ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

ENGINEERING AND TECHNOLOGY (IJARET)

ISSN 0976 - 6480 (Print) ISSN 0976 - 6499 (Online) Volume 4, Issue 6, September October 2013, pp. 27-39 IAEME: www.iaeme.com/ijaret.asp Journal Impact Factor (2013): 5.8376 (Calculated by GISI) www.jifactor.com

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PERFORMANCE OF INTEGRATED PROCESS USING FUNGAL STRAIN CORIALUS VERSICALOR (MTCC-138) IN MICROBIAL DYES DEGRADATION
B. Chirsabesan and M.Vijay* Department of Chemical Engineering, Annamalai University, Annamalai Nagar, Chidambaram -608002, India

ABSTRACT This work has been carried out for dyes degradation with the aim of investigating the effect of fungal strain Corialus versicalor ((MTCC-138) and increase process understanding in order to optimize the degradation reactions. From an applied experimentally based approach, membrane assisted electrochemical degradation and bio degradation of Quinoline Yellow, Eosin B and Rose Bengal dyes have been studied. The research was focused on using electrochemical equipment. . The specific degradation rates obtained showed that Corialus versicalor much more efficient in the decolourisation of dyes. This type of relation suggests that the decolourisation kinetics is energydependent. The free fungi cells of Corialus versicalor has the ability to reduce the percentage of COD more than 90% and to convert the effluent into reusable condition for the selected dye effluent with the aid of electro chemical oxidation at the specified conditions Key words: Corialus versicalor, Quinoline Yellow, Eosin B, dye degradation efficiency, current efficiency. 1. INTRODUCTION The process of biodegradation can be measured by monitoring any of the two factors, (1) by measuring the redox potential, together with pH and temperature, oxygen content and concentration of electron acceptors/donors as well as breakdown products such as carbon dioxide etc. (2) Measurement of chemical oxygen demand (COD) and biological oxygen demand (BOD). Biological oxygen demand represent only the organism matter which is being capable of degraded/oxidized by microbes where as COD represents all the oxidizable matters including organic matter in any particular effluent. In case of colored effluents, bioremediation is measured by estimating the decrease in color intensity. (Marmagne and Coste, 1996).

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

Although it is thought that some dyes are nearly non-biodegradable or un transformable by bacteria under aerobic condition, efforts to isolate bacteria capable of degrading dye have continued. Hu (1998) isolated Pseudomonas luteola from waste water treatment plant that decolorize reactive azo dyes. Wong and Yuen (1996) isolated a bacterium Klebsiella pneumoniae from dye contaminated sludge that could degrade the methyl red up to 100 mg l-1 more efficiently than other isolated bacteria. The ability of two bacterial strains, the Gram-negative Alcaligenes faecalis and the Grampositive Rhodococcus erythropolis to decolorize the monoazo dye Acid orange were studied with different initial dye concentrations by Mutafov et al. (2007). The azo dye and Reactive yellow 84A was efficiently degraded by a novel bacterial strain Exiguobacterium sp. White rot fungi can decolorize and degrade wide variety of azo dyes with the help of extracellular degradative enzymes. White rot fungi that produce lignolytic enzymes, such as lignin peroxidase, manganese peroxides and laccase have been studied extensively because of their ability to degrade various organic compounds (Fu and Viraraghvan, 2001)Decolorization of dyes normally begins with initial reduction cleavage of functional bond anaerobically, which results in colorless but toxic aromatic amines. This is followed by complete degradation of dyes under aerobic conditions. Therefore, anaerobic/aerobic processes are crucial for complete mineralization of organic dyes. However, not all bacteria have both anaerobic and aerobic properties. Usually consortia are routinely used for the degradation of azo dyes. Recent research has exposed the survival of wide variety of organisms in mixed culture capable of decolorizing a wide range of dyes. The complexity of the microbial consortium enables them to act on a variety of pollutants. Microbial consortia are usually used without analyzing the constituent microbial populations for environmental remediation (Mohorcic et al., 2004). Many reports indicate that textile industry effluent have toxic effect on the germination rates and biomass concentration (Wang, 1991). The toxicity of effluent is because of the presence of dye or its partially degraded product which are mutagenic or carcinogenic. Therefore the treatment of organic textile dyes becomes necessary prior to their final discharge to the environment (Kumar and Dastidar, 2009). Membrane-wet oxidation, an integrated process, has been demonstrated by Dhale and Mahajani (2000) to treat the disperse dye bath waste. On the other hand, these techniques do not eliminate definitively the dyes but only separate and concentrate them. The destruction of the concentrated pollutants requires an additional operation as incineration. However, as yet, there has not been a method employing the electrochemical oxidation process combined with the membrane filtration process for the treatment and reuse of textile dyehouse wastewater. The goal of this research is to study the performance of the arc-shaped transfer-flow membrane module, at the same time, to demonstrate these processes and to develop a potential dye wastewater treatment system for reuse The present study deals with studies on the Quinoline Yellow, Eosin B and Rose Bengal dyes decolorization by individual fungaistrains as well as membrane assisted electro chemical oxidation. Assessment of the removal efficiency of Quinoline Yellow, Eosin B and Rose Bengal dyes as well as its degradative capacity was also carried. 2. MATERIALS AND METHODS Analytical grade reagents of NaOH, Na2CO3, K2Cr2O7, H2SO4, Na2SO4, CH3OH, KBr, ferrous ammonium sulfate, ethyl acetateare used for all the analysis. Textile dye Quinoline Yellow, obtained from pollution control division, Central Electrochemical research Institute, Karaikudi, Tamilnadu. PES (3500) was received from Udel. Rose Bengal (C20H2Cl4I4Na2O5, Mr: 1017.65) was

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

procured from M/S Merck and the 0.01 M stock solution was the dye was prepared in doubly distilled water. Eosin B dye (4,5-Dibromo- 2,7dinitrofluorescein di sodium salt, colour index: 45400), chloroform, chlorosulfonic acid,methanol, and dimethylformamide (AR grade) were obtained from S.D fine Chemicals, India, and were used without any further purification. Fungal strain Corialus versicalor ((MTCC-138) was obtained from microbiology laboratory, Bharathidasan University, Trichy and used for the study. 2.1. Dye Effluent Preparation Dye concentration selected for experiments was 200 mg/L. This value is included in the range of real dye concentration found in textile effluents. Synthetic Quinoline Yellow, Eosin B and Rose Bengal dye bath effluent used in the present study was prepared according to the composition commonly used in cotton dyeing. In order to dye 0.1kg of fabric, 0.004 kg of dye is used. It is dissolved in 1 L of double distilled water along with the auxiliary chemicals such as 0.003 kg Na2CO3, 1 mL of NaOH 38B (44110-3 kgm-3NaOH solution)and0.01kg of NaCl. A 1.0.10-3 M solution of Rose Bengal was prepared as a stock solution, which was diluted further as and when required. The optical density of the Rose Bengal solution was determined using a spectrophotometer (Systronics model 106) at max = 550 nm. 2.2. Fungi Preparation 10mm Corialus versicalor ((MTCC-138) was taken from a fungal colony growingon potato dextrose plates and inoculated into 500 ml Erlenmeyerflasks with 100 ml N-limited medium. The flasks wereincubated statistically at 28C and flushed with pure oxygendaily for the study of laccase production. Fungai activitiesin the supernatant were determined at regular intervals.Unless otherwise indicated, carbon source, nitrogensource and inducers were added to the N-limited mediumto study their effects on laccase production. 2.3. Sulfonation of poly (ether ether ketone) The sulfonation of PEEK (Victrex PEEKTM 450PF powder) was prepared using concentrated sulfuric acid according to the following procedure. 2.3.1 Preparation of sulfonated poly (ether ether ketone) The 20 g of PEEK was dried in a vacuum oven at 100oC and then dissolved in 500 ml of concentrated (95-98% H2SO4) sulfuric acid at 50-70oC under vigorous mechanical stirring. The reaction time ranged from 5 to 6 h. The sulfonation reaction was terminated by decanting the polymer solution into a large excess of ice-cold water under continuous mechanical agitation and the polymer precipitate was filtered and washed several times with distilled water until the pH was neutral. The recovered SPEEK was dried at room temperature for 2 days, finally the polymer was dried in a vacuum oven at 80C for 24 h, and stored in a decicator (Jin et al 1985).

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

Table le 1: Chemical structure of organic dyes C.I.(Color Index) CAS registration number Quinoline Yellow Colour Index No.: 47005 Chemical Structure

Eosin B (disodium salt) CI Number: 45400

Rose bengal (disodium salt) CI Number: 45440

2.3.2. Characterization of sulfonated poly (ether ether ketone) The sulfonated sample was characterized for functional group determination by FT FT-IR Spectroscopy and Nuclear magnetic resonance (NMR) spectra. FT-IR IR spectra were recorded on a Perkin-Elmer, model-Spectrum Spectrum RX1 Fourier transform spectrometer either with powder samples inside a diamond cell or by using KBr pellets composed of 50 mg of IR spectroscopic grade KBr and 1mg polymer sample. 2.3.3. Preparation of Membranes SPEEK membrane was prepared by the diffusion induced phase separation method, namely, casting a thin film of the polymeric solution on a glass plate and, after allowing the solvent to evaporate e for a predetermined period at the desired humidity and temperature conditions, immersing it into a bath of non-solvent solvent (water, solvent, surfactant) for final precipitation. Prior to membrane casting, a gelation bath of 2L of distilled water (non-solvent), (non , containing 2% DMF (Solvent) and 0.2% SLS (Surfactant) was prepared and cooled to 10C. 2.3. Analytical methods The analytical methods used for this study are described below.
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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

2.3.1. Chemical Oxygen Demand (COD) In order to determine the extent of degradation degradation of the effluent Chemical Oxygen Demand (COD) was measured. The COD as the name implies is the oxygen requirement of a sample for oxidation of organic and inorganic matter. COD is generally considered as the oxygen equivalent of the amount of organic matter oxidizable by potassium dichromate. The organic matter of the sample is oxidized with a known excess of potassium dichromate in a 50% sulfuric acid solution. The excess dichromate is titrated with a standard solution of ferrous ammonium sulfate. COD of all samples were determined by the dichromate closed reflux method using thermo reactor TR620 TR620-Merck.In COD measurement, 3 samples are subjected to analysis for one COD data. From that, any two same values or the average of any two nearer values is cons considered as the measured data. 2.3.2. Spectral analysis using UV-visible visible spectrophotometer For UV-Visible Visible spectral analysis, 5 mL of treated and untreated samples were taken and centrifuged at 12,000 rpm for 10 min. The supernatant of untreated and treated samples were analyzed by monitoring the changes in its absorption spectrum using UVvisible UV visible spectrophotometer with a cell having 1 cm optical path length. 3. RESULTS AND DISCUSSION

3.1. Characterization of sulfonation of poly (ether ether ketone) The modification fication of polymers from hydrophobic in nature to hydrophilic is done by introducing polar groups on polymer backbones. Chemical modification of polymers is also used in many other applications to improve chemical resistance, enhance wear resistance and o others. Sulfonation of Poly (ether ether ketone) was preferred as a way to introduce polar groups (sulfonic acid groups) on this polymer. The introduction of sulfonic acid groups per repeating unit in the PEEK chain leads to an increase in its solubility. Sulfonation Sulfonation modifies the chemical character of PEEK, reduces the crystallinity and consequently affects solubility. The SPEEK could readily be dissolved in solvents that are not solvents for the original PEEK, such as DMF, acetone and NMP.

1081 cm-1

1655 cm-1

1253 cm-1

1025 cm-1

709 cm-1

Figure 1. Conformation nformation of sulfonation - Infra-Red Red Spectroscopy

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

The comparative FT-IR spectra of PEEK and SPEEK samples are shown in Figures 3.1 and 3.2. The broadband in SPEEK samples appearing at 3440 cm-1 was assigned to O-H vibration from solfonic acid groups. The aromatic C-C band at 1489 cm-1 for PEEK was observed to split due to new substitution upon sulfonation. A new absorption band at 1080 cm-1 in SPEEK was assigned to sulfur-oxygen symmetric vibration O=S=O. The new absorption at 1245, 1080 and 1020 cm-1, which appeared upon sulfonation were assigned to the sulfonic acid group in SPEEK (Ahmed et al 2012 and Mayahia et al 2013). 3.2. Physico-chemical characterization of dye samples The color, temperature and pH of the sample were recorded on the site and samples were transported to the laboratory by storage at 4C. Other physico-chemical characteristics like BOD, COD, etc. were measured on the same day of collection of sample. The same integrated electrochemical and biological oxidation method was used to degrade the simulated effluent containing bio recalcitrant synthetic dye with a well established fungal strain Corialus versicalor. In batch electro membrane reactor, electrochemical oxidation was carried out as a pretreatment before the biodegradation cycles to increase biodegradability and at the end as a post treatment to meet the required standards. Table 2. Performance of integrated process using free fungal strain Corialus versicalor (MTCC138) in microbial degradation
Parameters and Operating Conditions Batch Reactor holdup Initial COD Electrochemical Mediated Oxidation Charge input COD (after EMR with SPEEK membrane ) Biochemical oxidation Inoculums input COD (after inoculum addition) COD (after 120 h of aerobic oxidation) Electrochemical Mediated Oxidation Charge input COD (after EMR with SPEEK membrane) Biochemical oxidation Inoculum input COD (after inoculum addition) COD (after 120 h of aerobic oxidation) Electrochemical Mediated Oxidation Charge input COD (after EMR with SPEEK membrane) Biochemical oxidation Inoculums input COD (after inoculum addition) COD (after 120 h of aerobic oxidation) Post EMR with SPEEK membrane Overall COD Removal Units mL mg L-1 Ah L-1 mg L-1 mL L-1 mg L-1 mg L-1 Ah L-1 mg L-1 mg L-1 mg L-1 mg L-1 Ah L-1 mg L-1 mL L-1 mg L-1 mg L-1 mg L-1 (%) Environment I 200 2300 Cycle I 8 1800 8 1800 Environment II 200 2300

Using Corialus versicalor ((MTCC-138) 50 100 1900 2150 1450 1310 Cycle II 4 4 1220 1150 Using Corialus versicalor ((MTCC-138) 25 25 1300 1217 720 680 Cycle III 2 2 670 626 Using Corialus versicalor ((MTCC-138) 25 25 765 715 480 379 240 194 90.6 92.4

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

Biological oxidation was carried out in 3 cycles for two different initial inoculum concentrations at aerobic condition. In order to remove the microorganisms from the treated effluent and bringing the effluent to reusable form, photo oxidation method was carried out. The results are presented in the Figures 1 to 3 and Table 2. In 30 minutes of pretreatment of electro oxidation, it was observed that the COD decreased from 2300 mg L-1 to 1800 mg L-1 (22% reduction) for the applied charge of 1.6 Ah. This was found almost identical for all electro oxidation steps in different cycles, as well for post electro oxidation and all other electrolysis steps.

70 65

% of COD Remeoval Quinoline Yellow

60 55 50 45 40 35 30 25 20 15 10 5 0 0 20 40

Aerobic cycle I Anoxic Cycle I Aerobic Cycle II Anoxic Cycle II

60

80

100

120

140

160

Time (min)

Figure 2: Variation of %COD of Remeoval of Quinoline Yellow dye with time in 3 cycles for degradation of Corialus versicalor

Biodegradation process was a sequential one and it was carried out under both aerobic and anoxic conditions in two cycles of operation as indicated in Figure 1 to 3 for all dyes at 20 mL of inoculum containing Corialus versicalor ((MTCC-138). These Figures clearly indicate that there are remarkable changes in the course of the degradation process by Corialus versicalor by biochemical reaction. The COD reduction obtained for two degradation conditions (aerobic and anoxic) were 21% and 24% in first cycle and 36% and 23% in second cycles respectively for the effluent containing 20 mL of inoculum as observed from the Figure 1. Similarly from Figure 5.39 the COD reduction obtained for two degradation conditions (aerobic and anoxic) as 27% and 47% in first cycle and 30% and 23% in second cycle for the effluent containing 20 mL of inoculum respectively.

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

60 55 50 Aerobic cycle I Anoxic Cycle I Aerobic Cycle II Anoxic Cycle II

% of COD Remeoval Eosin B

45 40 35 30 25 20 15 10 5 0 0 20 40 60

80

100

120

140

160

Time (min)

Figure 3:Variation of %COD of Remeoval of Eosin B dye with time in 3 cycles for degradation of Corialus versicalor From Figure 3, the COD reduction obtained in the first degradation environments were 26.9% in the first cycle and 44.6% in the second cycle in aerobic and anoxic cycle respectively for the Eosin B dye effluent containing 20 mL of inoculums. Similarly from Figure 5.39 the COD reduction obtained for second degradation environments were 37.6% in the first cycle and 44.1% in the second cycle respectively for the rose Bengal dye effluent containing 20 mL of inoculums. As presented in Table 3, the overall % COD reduction obtained in the integrated process treatment of effluent containing dyes together with post electro membrane oxidation for the effluent containing 20 mL of inoculum is 92.4. The contribution of every stage and individual processes in integrated scheme for total COD reduction based on initial inoculum size of biodegradation. Though both the degradation environments gave almost identical total % COD reduction at the end of the integrated process, it can be seen that increase in molecular weight of dyes (375.3, 580.09 and 1017.64) could decrease %COD reduction up to 5% in biodegradation stages.

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

60 55 Aerobic cycle I Anoxic Cycle I Aerobic Cycle II Anoxic Cycle II

% of COD Remeoval of Rose bengal

50 45 40 35 30 25 20 15 10 5 0 0 20 40 60

80

100

120

140

160

Time (min)

Figure 4.Variation of %COD of Remeoval of Rose Bengal dye with time in 2cycles for degradation of Corialus versicalor The initial % COD removal of dyes was 3% at 30 minutes. As shown in the Figure 3, % COD removal increased and degraded in both process at 12 V of external potential supply. It is interesting to note that when both electrochemical membrane reaction and biodegradation were used effectively. This value is higher than the summation of the electrochemical and biodegrading process acting alone. In other words, the contribution of both processes has resulted in an increase of degradation by nearly 62.5%. Or the presence of both Corialus versicalor and PEM has enhanced the degradation by 37%. Such a synergetic effect between electro membrane reactor and bio degradation has been recognized by Luca et al. [5] at Nafion membrane and fungi using degradation of dyes. Conventional electrochemical process, electrolyte plays a very important role in the integrated photoelectrochemical process. As anions of the supporting electrolyte may participate in the decomposition reaction of dyes careful selection ofelectrolyte is essential in maximizing the degradation rate of given compound and minimizing the formation of toxic intermediates. Sodium chloride may electrochemically convert to chlorine, which may further react with intermediates to produce polychlorinated compounds. Comparatively, electro membrane reactor values are higher contribution than Bio degradation for Quinoline Yellow. However, bio degradations are higher contribution than electro membrane reactor in case of Eosin B dye solution. The reason is that Quinoline Yellow dye having low molecular weight of organic material capable of being oxidized, while the COD represents a more complete oxidation includes waste compounds that are difficult to breakdown with bacteria or compounds that are completely non-biodegradable. The membrane assisted electrochemical degradation method and biodegradation ismore suitable to be applied in final stage of wastewater treatment where effluents have undergone pretreatment. Thus, membrane assisted electrochemical process should be used to complement the conventional methods such as coagulation flocculation and biological treatment to ensure complete mineralisation of the textile wastewater.
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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

3.3. Modified Integrated Dye Degradation Process for dyes In this study, a modified combination method has been tried to treat the synthetic effluent containing Quinoline Yellow and Rose Bengal dye. Table 3. Contribution of every stage and individual processes in integrated scheme when Corialus versicaloris used in microbial degradation Contribution of Dyes at 20mL inoculums Stage Quinoline Yellow Eosin B (disodium salt) 30.65 19.98 8.85 19.94 2.29 10.46 7.83 49.62 50.38 Rose bengal (disodium salt) 28.4 20.5 9.85 11.5 2.5 9.56 5.67 45.6 53.45

EMR Cycle I 31.26 Bio degradation Cycle I 16.93 EMR Cycle II 10.36 Bio degradation Cycle II 20.73 EMR Cycle III 2.16 Bio degradation Cycle III 8.20 Post EMR 10.36 Contribution of Individual processes Electrolysis 54.15 Bio degradation 45.85

The prepared dye effluent was sequentially fed in to electrochemical membrane reactor for 4 h followed by different microbial batch reactors at aerobic conditions using fungal strains (Corialus versicalor) and then again electrochemical membrane reactor for 5 h in sequence 3.4. Electrochemical Pretreatment Due to 4 h of pre electro oxidation, COD of the effluent reduced from 2556 mg L-1 to 1370 mg L-1 (46%) for the applied charge of 3.84 Ah. The greater %COD reduction inmicrobial oxidation may be obtained by increasing the degradation time in pre electrochemical methods to enhance the biodegradability. 3.5. Microbial Oxidation Microbial oxidation using two fungal strains were carried out for 120 h for the electrochemically pre treated dye effluent. The results are shown in Table 4. The COD of the effluent reduced for the increasing degradation time for all the micro organisms. At the end of 120 h, the maximum COD reductions obtained was 33%, for the effluent containing both bacterial strain Corialus versicalor. It can be noted from Table 5.7, at the end of 4 h of pre electro membrane oxidation, COD of the initial effluent was reduced from 2305 mg L-1 and 2350 for Quinoline Yellow and Rose Bengal dye. The value reduced to 1370 mg L-1and 1830 for respective dyes for the applied charge of 3.84 Ah in PEM (SPES and SPEEK) membranes. In addition of 50 mL of inoculum (broth containing bacterial strain) to 150 mL of effluent the COD value is increased in the entire stream due to presence of biomass and its growth. In case of the fungi strain, Corialus versicalor, the COD value increases from 1370 mg L-1 to 1734 mg L-1 due to the increase in bacterial concentration, and it reduced to 1340 mg L-1 due to 120 h of biochemical oxidation, while the Rose Bengal dyeis considered, the COD value increases from 2150mg L-1 for Corialus versicalor.
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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

Table 4. Performance integrated process using fungal strains in microbial degradation Parameters and Operating Units Environment Conditions Pollutant Initial COD Quinoline Yellow Rose Bengal dye mgL 2305 2350 Electrochemicalmembrane Pre treatment Batch Reactor holdup mL 400 400 -1 Charge input AhL 9.6 9.6 COD (after Electro Oxidation) mgL-1 1370 1830 Biochemical oxidation Fungi Corialus R. arrhizus Corialus R. arrhizus versicalor versicalor Effluent Volume mL 200 200 200 200 Inoculums Volume mL 50 50 50 50 Batch Reactor holdup mL 300 300 300 300 COD (after inoculum mgL-1 1340 3500 1650 2150 addition) COD (after 120 h of mgL1026 1734 1225 952 1 aerobic oxidation) Electrochemical MembranePost treatment Batch Reactor holdup mL 300 300 300 300 Charge input AhL-1 12 12 12 12 -1 COD (after Electro mgL 580 420 640 360 Oxidation) Photo catalytic oxidation Batch Reactor holdup mL 300 300 300 300 -1 COD (after Electro mgL 215 153 280 160 Oxidation) Overall COD Reduction 91.8 94.2 95.4 93.8 (%)
-1

and it reduced to 1650 for Corialus versicalor due to growth of biomass and after 120 h of biochemical oxidation it reduced from to 1225 mgL-1and 952. Increased biomass concentration is responsible for effective degradation. 3.6. Post Electrochemical membrane Oxidation The biologically treated effluent streams subjected to electro chemical membrane oxidation for 5 hours. The % COD reduction increases when time proceeds, for all effluent streams as shown in Table 5.8. The maximum COD reductions obtained at the end of 5 h for the effluent streams incubated with the fungi strain Corialus versicalor, in biochemical oxidation. The minimum COD reduction of 19% was observed for the effluent incubated with the fungal strain Corialus versicalor. 3.7. Photo catalytic oxidation The electro chemically treated effluent streams were subjected to membrane and photo cataylytic oxidation for 5 h. The observed results are shown in Table 4. The %COD reduction
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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

increases when time proceeds for all effluent streams. The maximum COD reductions obtained at the end of 5 h of photo catalytic oxidation are COD of the effluent reduced from 580 mg L-1 to 215 mg L-1 and COD of the effluent reduced from 640 mg L-1 to 280 mg L-1for the effluent streams incubated with the fungal strain Corialus versicalor for Quinoline Yellow in microbial oxidation respectively. According to earlier reports of Alinsafi et al. (2007), Konstantinou and Albanis (2004), Neelavannan et al. (2007) and Neelavannan and Ahmed Basha (2007), when TiO2 is illuminated by light ( <390 nm) electrons are promoted from the valence band to the conduction band to give electron-hole pairs. 3.8. Overall % COD Reduction in Different Treated Effluent Streams The overall COD reductions obtained at end of the sequential study for the different effluent streams containing dye Quinoline Yellow and Rose Bengal dye are 91.8% and 95.4% for respectively to the effluent streams containing fungal strain Corialus versicalor. The reductions values of 94.2%, and 93.8% in COD were obtained for the Rose Bengal dye effluent streams incubated with the fungal strain Corialus versicalor in microbial oxidation. CONCLUSION The dye stuffs and dye waste water from textile industry has created environmental pollution as well as medical and aesthetic problems associated with human health and agriculture, thus bioremediation of contaminated site is of prime importance. The difference in decolorization capacity of different organic dyes by fungi was due to dissimilarity in specificities, structure and complexity, and the interaction with functional bond with different dyes. Such biological processes could be adopted as apre-treatment decolorization step, combined withmembrane assisted electro oxidation and biological process to reduce the BOD and COD, as an effective alternative for use by the textile-dyeing industries. The techniques by which decolorization occurs vary and among them biodegradation seems of great significance for future development in bio-removal or bio-recovery of dye substances REFERENCES 1. 2. 3. 4. Marmagne, O. & Coste, C. (1996). Color removal from textile plant effluents. American dyestuff reporter. Hu, T.L. (1998). Degradation of azo dyes RP2B by Pseudomonas Luteola. Water Science Technology. 38: 299-306 Wong, P.K. and Yuen, P.Y. (1996). Decoilorization and biodegradation of Methyl Red by K. pneumonia RS13. Water research. 30: 1736 1744 Mutafov, S., Avramova, T., Stefanova, L., Angelova, B. (2007). Decolorization of acid orange by bacteria of different tinctorial type: a comparative study. World J. Microbiol Biotechnol. 23: 417 422. Fu Y., Viraraghavan T. (2001). Fungal decolorization of dye wastewaters: a review, Bioresour Technol. 79: 251-262 Mohorcic, M., Friedrich, J., Pavko, A. (2004). Decolorization of the diazo dye reactive black 5 by immobilized Bjerkandera adusta in a stirred tank bioreactor. Acta Chim. Slov. 51: 619628 Kumar K, Dastidar, M. G., Sreekrishnan, T. R. (2009). Effect of process parameters on aerobic decolourization of reactive azo dye using mixed culture. World academy of science, Engineering and Technology. 58:962-965 Wang, W. (1991) Toxicity assessment of pretreated industrial effluent using higher plant. Research Journal Water Pollution Control Federation. 62: 853 860.
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5. 6.

7.

8.

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9. 10. 11.

12.

13.

14.

15.

16.

Lucas, M.S. and J.A. Peres (2006) Decolorization of the azo dye Reactive Black 5 by Fenton and photo- Fenton oxidation. Dyes. Pigm., 71, 236-244 Dhale AD and Mahajani VV (2000) Studies in treatment of disperse dye waste: membranewet oxidation process. Waste Manage. 20, 125-138 A. Mayahia, A.F. Ismail, H. Ilbeygi, M.H.D. Othman, M. Ghasemi, M.N.A.M. Norddin, T. Matsuura, Effect of operating temperature on the behavior of promising SPEEK/cSMM electrolyte membrane for DMFCs, Separation and Purification Technology 106 (2013), 7281. A.A.Ahmed, A.S. Sultan, S. M. J. Zaidi, Sulfonated Poly(Ether Ether Ketone) (SPEEK): A Promising Membrane Material for Polymer Electrolyte Fuel Cell, Ion Exchange Technology I, 2012, 437-451. V.C.Padmanaban, Soumya.S.Prakash, Sherildas P, John Paul Jacob and Kishore Nelliparambil, Biodegradation of Anthraquinone Based Compounds: Review, International Journal of Advanced Research in Engineering & Technology (IJARET), Volume 4, Issue 4, 2013, pp. 74 - 83, ISSN Print: 0976-6480, ISSN Online: 0976-6499. Syed Abdul Moiz and Ahmed M. Nahhas, Temperature Dependent Electrical Response of Orange-Dye Complex Based Schottky Diode, International Journal of Electronics and Communication Engineering & Technology (IJECET), Volume 4, Issue 2, 2013, pp. 269 - 279, ISSN Print: 0976- 6464, ISSN Online: 0976 6472. Kh. EL-Nagar and Mamdouh Halawa, Effect of Mordant Types on Electrical Measurements of Cotton Fabric Dyed with Onion Scale Natural Dye, International Journal of Electrical Engineering & Technology (IJEET), Volume 3, Issue 2, 2012, pp. 192 - 203, ISSN Print : 0976-6545, ISSN Online: 0976-6553. B. J. Agarwal, Eco-Friendly Dyeing of Viscose Fabric with Reactive Dyes, International Journal of Advanced Research in Engineering & Technology (IJARET), Volume 1, Issue 1, 2010, pp. 25 - 37, ISSN Print: 0976-6480, ISSN Online: 0976-6499.

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