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& IWA Publishing 2011 Water Science & Technology 9 63.4 9 2011

Photoeletrolytic system applied to remazol red brilliant degradation

Mariana Lopes Sousa, Peterson Bueno Moraes and Ederio Dino Bidoia

ABSTRACT
Toxicity tests using Sacharomycces cerevisiae were made with simulated textile efuents containing reactive dye (remazol red brilliant) treated by photoeletrolytic process, varying treatment time and applied current. The treatment incorporated an electrolytic reactor with rectangular titanium anode coated with 70% TiO2/30% RuO2 cathode and a rectangular stainless steel coupled with another photolytic reactor containing a high power UV lamp. The treatment system was used in batch recirculation, in other words, the simulated efuent was driven by the system through a helical pump. It was observed that the higher the value of current applied, the longer the treatment has greater color removal of textile efuent and higher mortality of S. cerevisiae, killing up to 100% of the cells at the end of the treatment. With a lower current applied and having the treatment time of 5 minutes, the efuent showed a color removal of 97% and a lower mortality of S. cerevisiae than the efuent simulated without any treatment.
Key words 9 remazol red brilliant, Saccharomyces cerevisiae, photoeletrolytic treatment, toxicity,
Mariana Lopes Sousa Universidade Estadual Paulista(UNESP), IB - Rio Claro, SP Brazil Peterson Bueno Moraes Dr., Universidade de Campinas (UNICAMP), CESET - Limeira, SP - Brazil Ederio Dino Bidoia (corresponding author) Universidade Estadual Paulista (UNESP), Rio Claro, Sao Paulo, Brazil Email: ederio@rc.unesp.br

textile efuent

INTRODUCTION
Each day, a high volume of water is contaminated by the textile industry (Georgiou et al. 2002). The textile industry is very important in global economy but there is still a gap between environmental responsibilities. In Brazil where the textile industry has a large market share but also areas that suffer from shortages of water, a study by Abreu et al. (2008) showed that the investments in pollution control were not done by social and environmental concern; they were made to avoid nes and to obtain government grants. Textile wastewater is highly colored because of the dyeing step (Kunz & Peralta-Zamora 2002). This wastewater is inappropriate for human consumption and survival of aquatic species, because it reduces the processes of photosynthesis due to water turbidity (Robinson et al. 2001; Catanho et al. 2006a). Also, the treatment applied to these wastewater is often unable to remove dyes coloration or degrade toxic substances presented in efuents (Gusmao et al. 2009) like mutagenic and carcinogenic substances or heavy metals (Akyol & Bayramoglu 2005; Catanho et al. 2006a). Therefore it promotes an imbalance in aquatic ecosystems (Georgiou et al. 2002).
doi: 10.2166/wst.2010.208

About 60% of dyes used in textile industry belongs to the sulphonated vinyl reactive group, with chromophore azo group N N (Catanho et al. 2006a). These dyes are highly soluble in water and usually have a high discharge rate (percentage of dye that does not bind the bers and is released in the efuent) reaching up to 50% of discharge (Al-Degs et al. 2000). Thus, the higher the concentration is, the more difcult it is to remove the dye from the water (Korbahti 2007). The reactive dyes are formed by strong bonds, due to the azo chromophore group, which is not disrupted by biological processes; which leaves an inefcient outcome with this type of efuent, especially regarding color removal (Al-Degs et al. 2000; Araujo & Yokoyama 2006). Biological treatment methods use fungi and bacteria for biosorption and biodegradation of these compounds in efuents (Beydilli et al. 2000; Aksu 2001; Machado et al. 2006). As an alternative to biological processes, there are physical and chemical processes, such as: electrolytic processes (Osugi et al. 2003), UV oxidation (Georgiou et al. 2001; Akyol & Bayramoglu 2005), hydrogen peroxide (Catanho et al. 2006b), Fenton system (Robinson

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Water Science & Technology 9 63.4 9 2011

et al. 2001) and photoeletrolytic system, which unites an electrolytic reactor and a UVC light in a single treatment. During electrolysis, the pollutants can be degraded by direct electrolysis, where the charge transferred on the surface of the anode destroys pollutants (Chiang et al. 1995), or by indirect electrolysis, which is added a chemical compound that can generate oxidizing agent in the solution (Chiang et al. 1997) and the UV lamp does the reactions faster and optimizes the process by oxidation (Robinson et al. 2001). However, physical and chemical processes are able to either destroy the dye molecule completely to carbon dioxide, or only transform it, enduring in the efuent as an alternate form (Sauer et al. 2002). The objective of this study is to do an effective treatment for reactive dyes, resulting in removal of both color and toxic compounds in efuents containing reactive dyes using the photoeletrolytic process, in this case, Remazol Brilliant Red (CI reactive red 21) and measure the toxicity of the treated efuent using the yeast Sacharomycces cerevisiae.

FM

L R F P: Pump R: Reservoir FM: Flow Meter L: UVC Lamp E: Eletrolytic Reactor F: Faucet

Figure 1 9 Scheme of photoeletrolytic system.

MATERIALS AND METHODS

The photochemical treatment system was composed of a photolytic reactor which was a chamber of stainless steel with a UVC lamp (Germetec model FPG-MP - 1600 W) connected the electrolytic reactor that was composed of a rectangular titanium anode coated with 70% TiO2/30% RuO2 cathode and a rectangular stainless steel. These two systems work at the same time. It was used an electrical current of Instrutherm - FA-2030 to polarize the electrodes. (Figure 1) Into a 4 L ask was added 40 g of sodium chloride (10,000 ppm) (Merck P.A.) and 5.28 g of anhydrous sodium carbonate (Chemis P.A.), and these reagents were mixed with 4 L of distilled water, and after that 0.8 g of dye powder was added slowly into the solution, with a nal concentration of 200 ppm. This concentration is based on studies of Catanho et al. (2006a) and Georgiou et al. (2002). Actually it was used a higher concentration than these studies, that were of 30 ppm and 100 ppm respectively. The dye was produced by ShangHai Titanchem Ltda. (China) and it is known commercially as remazol red brilliant (CI reactive red 21). Its chemical formula is C19H10Cl2N6Na2O7S2 (Figure 2) and it called disodium salt of 2,7-Naphthalenedisulfonic acid, 5-[(4,6-dichloro-1,3,5triazin-2-yl)amino]-4-hydroxy-3-(phenylazo). The pH of the prepared solution was about 10.5, so it was necessary to acidify it, because, according to Sauer et al. (2002), the titanium anode coated with 70% TiO2/30% RuO2

has a better efciency in acid pH due to the surface charge of TiO2 (pzc is close to 6.8). It was used sulfuric acid 2 M to achieve pH around 3.5. This simulated efuent was exposed to continuous currents of 3 A, 5 A and 7 A. Samples were taken in pre-determined times: zero minute (simulated efuent without treatment), 3 minutes, 5 minutes, 15 minutes and 30 minutes. The UV-C light was turned on for 3 minutes at the beginning of any treatment (3, 5, 15 or 30 min). Due to the high heat liberated by the UVC Lamp, it was turned on for a few minutes. Samples were stored and maintained under refrigeration for later analysis of absorbance (spectrophotometer Shimadzu UV-2401PC), pH (Digimed DMPH-2) and toxicity using S. cerevisiae. The chemical and toxicity analysis were performed when the samples were collected and 15 days later for complete stabilization. Toxicity tests were made according to Regis & Bidoia (2001) and this method constitute on exposure of the S. cerevisiae suspension directly to the efuent. The S. cerevisiae
CI N OH N O Na+ O N O S O O
Figure 2 9 Structure of Remazol Red Brilliant.

N N CI

HN

Na+

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Water Science & Technology 9 63.4 9 2011

suspension was prepared with 7.5 g of yeast from Fleischmann Royals dissolved in 100 mL of distilled water. Later, this cell suspension was centrifuged at 5,000 rpm with the centrifuge MLW model K24. The supernatant was discarded and the yeast cells were resuspended with 100 mL of distilled water. This mixture was centrifuged two more times in order to obtain 1.0 g of cells/mL or 1.2 109 cells cm3. The S. cerevisiae cell has a cellulolytic cell wall that is very resistant to osmotic variation. It was prepared test tubes in triplicate containing 9 mL of simulated efuent (a control tube was also made containing only distilled water) and 1 mL of the S. cerevisiae suspension. After that the tubes were incubated in BOD chamber (Marconi MA-403) at 281C for 3 days. Each tube was homogenized and it was taken 0.5 mL from them and this solution was added to another tube containing 0.5 mL of erythrosine solution, which is a red dye. The erythrosine is not able to stain living cells of S. cerevisiae but it indicates the dead cells stained red in microscopy. The living cells remained seethrough, but their contours were clearly visible, which makes their identication possible. The toxicity was analyzed in a Neubauer chamber at microscopy counting living and dead S. cerevisiae cells.

200 Dye concentration / mg L1 3A 5A 7A

150

100

50

0 0 5 10 15 20 25 30

Treatment time / min

Figure 3 9 Dye concentration after 15 days rest in different currents.

RESULTS AND DISCUSSION

The process proved itself extremely successful in color removal from the solution when sodium chloride 10,000 mg L1 was used as electrolyte. When exposed to 15 minutes treatment and after 15 days rest, the simulated efuent color disappeared completely in all essays (Figure 3). This means that the chromophore groups were modied, due to the chloride ion that was able to break the bonds of the azo chromophore group (Szpyrkowicz et al. 2005). But the dye molecule remained in solution in a modied structure with absorbance in ultraviolet region (Sauer et al. 2002). It is important to note that these absorption data were obtained after the samples were left in refrigerator for 15 days, as a time for stabilization. During this time there is a intermediate formation of oxidants in the solution as chlorine (Cl2) by oxidation of chloride (Cl) in electrolysis, and also formation of OH radical and H2O2 (Sauer et al. 2002) when the simulated efuent was irradiated by UVC light for 3 minutes. Irradiation periods higher than 3 minutes increased heating in system, which could harm the photoelectolytic system. Also, more than 3 min leads to high toxicity to the efuent. The treated efuent in photoeletrolytic system left for 5 minutes (7 A current) had a total color removal, remaining

colorless after 15 days rest. It was observed that a high quantity of chlorine was formed with the highest 7 A current. These compounds destroyed the chromophore groups during the photoeletrolytic treatment (Sauer et al. 2002; Szpyrkowicz et al. 2005). However, the treatment of 5 minutes using 5 A current did not completely remove the color right after treatment, but after 15 days rest the color disappeared (Figure 2). This is due to formation of reactive substances with residual effects, such as chlorine dissolved in water. The Cl2 concentration in this essay was lower than the 7 A essay, but this lower concentration chlorine formed at 5 A treatment acted gradually oxidizing the chromophore groups during the 15 days rest. In essays using 3 A current, the color was not completely removed in 5 minutes, even after 15 days (Figure 3), i.e., there was not enough oxidants to degrade the dye molecules. The simulated efuent had an initial pH around 10.5 and 3.0 to 3.5 after being acidied. In Figure 4 was shown the pH values after 30 minutes treatment in different currents: 3 A, 5 A and 7 A. The pH values obtained after the solution kept 15 days of rest for stabilization were 3 A (6.7), 5 A (7.0) and 7 A (7.15) and they are a little different from the pH after the electrolysis shown in the Figure 4. Toxicological tests were done using the S. cerevisiae as a test organism and provided information about various aspects of photoeletrolytical degradation (Figure 5). Initially, high toxicity causes 100% of cell mortality in efuent treated for 30 minutes to all currents (3 A, 5 A and 7 A) right after the treatment. This was due to chlorine dissolved in water formed during electrolysis (Korbahti 2007), which is very oxidizing and has residual effects (Russell 1992). Chlorine presence was identied by qualitative analytical test using o-toluidine reagent, which in contact with the chlorine solution becomes

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Water Science & Technology 9 63.4 9 2011

7.0 6.5 6.0 5.5 pH 5.0 4.5 4.0 3.5 0 5 10 15 20 25 30 3A 5A 7A

chlorine and, after rest, there was a quite noticeable reduction in toxicity. As the average toxicity decreased in 5 minutes treatment to 5% and the mortality of S. cerevisiae cells in simulated efuent without treatment was about 7%, due to the inherent toxicity of the remazol brilliant red. It can be concluded that the treatment of 5 minutes decreased the toxicity of the efuent as a result of changes in the dye molecule.

CONCLUSIONS
The total color reduction at the day of treatment only occurred after 30 minutes. During this time period there was high mortality of S. cerevisiae cells due to the chlorine formed. For 5 minutes essays after 15 days rest there was a lower mortality of S. cerevisiae cells even in relation to the simulated efuent without treatment along with the fact that the efuent became almost colorless (97% of color removal). Thus, the efuent needed to be stored for a period to achieve the reduction of toxicity and color desired. The pH remained acid, and should be equalized to 7 with addition of base. Therefore, the optimum treatment was for 5 minutes, under a current of 3 A, with 10,000 mg L1 of sodium chloride and the efuent needs a 15 days rest. This system presented a signicant removal of color (97%) and had lower toxicity than the simulated efuent without treatment.

Treatment time / min

Figure 4 9 Efuent pH in different currents.

yellow (APHA 1998). Toxicity test after 15 days indicated a decrease in chlorine residual effect because more cells remained alive. After 15 days of 30 minutes treatment, the samples treated by 5 A and 7 A current also showed high toxicity with a rate of 100% of death in microorganisms (Figure 5). In the 3 A essay, the toxicity was lower (36%), but the solution was still toxic. Consequently, the mortality of cells increases with higher currents, because more Cl was transformed into Cl2 (Russell 1992). In Figure 5, it was demonstrated that 5 minutes essays obtained a good amount of color removal and lower toxicity when the sample was collected right after the treatment for all currents (3 A, 5 A and 7 A), with toxicity of 11.5%, 65% and 68.5%, respectively. After 15 days rest, the cell mortality dropped to 4.0% in 3 A, 5.9% in 5 A and 6.0% in 7 A. This indicates that a lower time of electrolysis produces less

ACKNOWLEDGEMENTS
The support of CNPq-PIBIC and UNESP is gratefully acknowledged.

100 80 % Dead cells 60 40 20 0 0

3A 5A 7A

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10 15 20 Treatment time / min

25

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Figure 5 9 Efuent toxicity by S. cerevisiae cells after 15 days rest in different currents.

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