The objectives of this study were to determine the physico-chemical characterization of Magenta printing effluent treated with homogeneous Fenton process, as well as kinetic model that best describes degradation process of organic pollutant. Physico-chemical characterization of printing effluent before and after homogeneous Fenton treatment included measurements of pH, electrical conductivity, temperature, turbidity, chemical oxygen demand, biochemical oxygen demand, total organic carbon and toxicity test. Three kinetic models (first-order, second-order, and Behnajady-Modirshahla-Ghanbary) were evaluated in order to best describe Magenta degradation process. Results indicated that dye degradation process is followed with the increase of conductivity and biological oxygen demand due to the formation of various by-products and release of inorganic ions. The obtained results are in accordance with the established dye mineralization degree on the basis of chemical oxygen demand and total organic carbon content. However, treated printing effluent is characterized as nontoxic due to the Vibrio fischeri inhibition of 18.16%

Bečelić-Tomin, Milena

Dalmacija, Bozo

Gvoić, Vesna

Kerkez, Đurđa

Kulić Mandić, Aleksandra

Leovac Maćerak, Anita

Prica, Miljana

Gvoić Vesna

Prica Miljana

Kerkez Đurđa

Bečelić-Tomin Milena

Kulić Mandić Aleksandra

Leovac Maćerak Anita

Dalmacija Bozo

University of Szeged

 25th International Symposium on Analytical and Environmental Problems 141 CHARACTERIZATION AND KINETIC STUDY OF MAGENTA PRINTING EFFLUENT AFTER HOMOGENEOUS FENTON TREATMENT  Vesna Gvoić1, Miljana Prica1, Đurđa Kerkez2, Milena Bečelić-Tomin2, Aleksandra Kulić2, Anita Leovac Maćerak2, Božo Dalmacija2  1Department of Graphic Engineering and Design, University of Novi Sad, Faculty of Technical Sciences,Trg Dositeja Obradovića 6, 21000 Novi Sad, Serbia  2Department of Chemistry, Biochemistry and Environmental Protection, University of Novi Sad, Faculty of Sciences, Trg Dositeja Obradovića 3, 21000 Novi Sad, Serbia e-mail: kecic@uns.ac.rs  Abstract The objectives of this study were to determine the physico-chemical characterization of Magenta printing effluent treated with homogeneous Fenton process, as well as kinetic model that best describes degradation process of organic pollutant. Physico-chemical characterization of printing effluent before and after homogeneous Fenton treatment included measurements of pH, electrical conductivity, temperature, turbidity, chemical oxygen demand, biochemical oxygen demand, total organic carbon and toxicity test. Three kinetic models (first-order, second-order, and Behnajady-Modirshahla-Ghanbary) were evaluated in order to best describe Magenta degradation process. Results indicated that dye degradation process is followed with the increase of conductivity and biological oxygen demand due to the formation of various by-products and release of inorganic ions. The obtained results are in accordance with the established dye mineralization degree on the basis of chemical oxygen demand and total organic carbon content.  However, treated printing effluent is characterized as nontoxic due to the Vibrio fischeri inhibition of 18.16%.  Introduction In last two decades, researchers have emphasized the use of advanced oxidation processes (AOPs) as techniques that take prominence among various treatments, in order to reduce the concentration of inorganic and organic pollutants in industrial effluents. The advantages of these processes are reflected in the generation of hydroxyl radicals (HO•), powerful oxidizing agents, with a pronounced tendency for degradation of difficult biodegradable compounds, or transformation of pollutants into less toxic products of small molecular weight through rapid and non-selective radical reactions. The most commonly AOPs used in wastewater treatment are ozonization, photocatalysis, electrochemical oxidation, Fenton and Fenton-like processes [1]. In our previous work [2], the homogeneous Fenton process (FeSO4/H2O2 treatment) was applied in order to examine the possibility of Magenta dye removal from flexo printing wastewater. The process was optimized and maximum decolorization efficiency of 95.91% was achived. The aim of this study was to determine physico-chemical characterization of Magenta printing effluent treated with homogeneous Fenton process. Further more, three kinetic models were used to describe degradation process of Magenta dye in printing effluent.   Experimental Materials. Experiments were performed on Magenta printing effluent obtained from flexographic printing facility located in Novi Sad, Serbia. Magenta dye (C.I.: PR57:1, CAS number: 5281-4-9, chemical formula: C18H12N2O6, molar mass: 352 g/mol; λmax = 573 nm) was produced from Flint Group and belongs to the group of azo dyes.   25th International Symposium on Analytical and Environmental Problems 142 Physico-chemical analysis of printing effluent before and after Fenton treatment. Physico-chemical characterization of printing effluent before and after homogeneous Fenton treatment included determination of pH, electrical conductivity, temperature (AD110 Adwa instrument), turbidity (Turb 430 IR WTW), chemical oxygen demand (COD), biochemical oxygen demand (BOD), total organic carbon (TOC) (LiquiTOC II - Elemental, Germany), as well as toxicity evaluation. COD measurement was conducted using the potassium dichromate volumetric method - SRPS ISO 6060: 1994 [3]. Determination of BOD after 5 days at 20 °C was carried out by the manometer method - H1.002 (Velp Scientifica Italia, Lowibond and WTW), while the method SRPS ISO 8245:2007 [4] was used to determine the TOC value, which was used to estimate the mineralization degree of treated effluent according to the equation (1):      𝑇𝑂𝐶 (%) =  𝑇𝑂𝐶0−𝑇𝑂𝐶𝑇𝑂𝐶0∗ 100                          (1)  where: TOC0 represent total organic carbon content in the printing effluent before the homogeneous Fenton treatment, and TOC is the total organic carbon content in the printing effluent after the homogeneous Fenton treatment. Determination of anionic surface active substances (dodecylbenzene sulfonate - DBS) was measured by the index of methylene blue spectrophotometric method based on SRPS EN 903:2009 [5]. Chloride content was determined according to ISO 9297/1: 2007 [6], while the phosphorus content was determined with spectrophotometric method with ammonium- molybdate according to the SRPS EN ISO 6878:2008 [7]. Standard ISO 11348-3:2009 method was applied to test the toxicity of printing effluent before and after treatment, in order to evaluate negative impact of printing wastewater on living organisms [8].  Kinetics of homogeneous Fenton process. Numerous mathematical models have been used to describe the degradation kinetics of organic pollutants, based on the equilibrium state approximation. The main assumptions are based on the facts that the concentration of HO• radicals is correlated with the concentration of hydrogen peroxide, or that the HO• radicals formation rate is equal to their consumption rate  [9, 10]. Since the whole dye degradation process cannot be described by simple kinetic model, the first-order, second-order and Behnajady-Modirshahla-Ghanbary (BMG) models were used to study Magenta degradation kinetics by the homogeneous Fenton oxidation process [11, 12]. The mathematical models of the first and second order reaction kinetics, as well as the BMG model are present in equations 2 - 4 [13]:  𝑑𝐴𝑡𝑑𝑡= −𝑘1𝐴𝑡                  (2) 𝑑𝐴𝑡𝑑𝑡= −𝑘2(𝐴𝑡)2               (3) 𝐴𝑡𝐴0= 1 − ( 𝑡𝑚+𝑏𝑡)              (4)  where A0 and At represent the initial dye absorbance over a period of time from zero to t, k1 and k2 are the first and second order constants, while b and m are the BMG model constants, related to the reaction kinetics and oxidation capacity, respectively. The parameters of kinetic models were calculated using linear forms of first- and second-order mathematical models, as well as BMG models (equations 5 - 7):         𝐴𝑡 = 𝐴0 ∗  𝑒−𝑘1𝑡                  (5)  25th International Symposium on Analytical and Environmental Problems 143       1𝐴𝑡= 1𝐴0+ 𝑘2𝑡                   (6) 𝑡1−𝐴𝑡𝐴0= 𝑚 + 𝑏𝑡                         (7)  By plotting the dependence graphs ln(A0/At) in function t for the first-order model, (1/At) in function t for second-order model and t/1-(At/A0) in function t for BMG model, the kinetic model parameters were calculated and used to interpret the kinetics of the observed reactions.  Results and discussion The obtained values of physico-chemical parameters (Table 1) indicate that homogeneous Fenton treatment is characterized with the conductivity and BOD increase, pointing to the formation of numerous degradation by-products. The experimental results indicate that the mineralization percentage of Magenta dye of 49.82% is followed with 71.44% of COD reduction (Figure 1). On this basis, Magenta dye degradation resulted within the formation of low molecular weight fragments during the homogeneous Fenton process.   Table 1. Physico-chemical characterization of printing effluent before and after treatment Parameter Printing effluent Treated printing effluent pH 7.60 7 Conductivity [µScm-1] 403 560 Temperature [°C] 22.1 22.6 Turbidity [NTU] 18.81 10.3 COD [mgO2L-1] 377.7 107.87 BOD [mgO2L-1] 5 27 TOC [mgCL-1] 166.4 83.49 DBS [mgL-1] 0.77 <0.1 Phosphate [mgPL-1] <0.011 <0.011 Chlorides [mgClL-1] 21.60 22.30     Figure 1. Mineralization degree of printing effluent after homogeneous Fenton treatment  The results of acute toxicity test on Vibrio fischeri bacteria (Table 2) indicated slightly increased toxicity of treated printing effluent after homogeneous Fenton process. This percentage of inhibition falls within the range below 50%, confirming that the treated printing effluent is nontoxic.  25th International Symposium on Analytical and Environmental Problems 144 Table 2. Results of toxicity test by Vibrio Fischeri inhibition Sample GL Inhibition (%) Wastewater before Fenton treatment 4 15.11 FeSO4/H2O2 treatment 2 18.16  The results of the kinetic studies used to analyze the Magenta dye degradation in printing effluent are presented in Table 3 and Figure 2. The highest values of correlation coefficient were established using the BMG model, which best describes the dye degradation process.  Table 3. Kinetic parameters of selected models for Magenta dye degradation Model First-order Second-order aBMG model Process K1 (min-1) R2 K2 (l mg-1min-1) R2 b m 1/m R2 FeSO4/H2O2 0,031 0,649 0,062 0,602 0,905 18,439 0,054 0,986 aBehnajady-Modirshahla-Ghanbary model    Figure 2. Decolorization kinetics of printing effluent under optimal process conditions - BMG model  Linear plot of t/(1−At/A0) versus t was used to determine the parameters b and m, which describes the oxidizing capacity and the initial rate of decolorization reaction, respectively. Based on R2 value, chosen model offers satisfactory interpretation of the kinetic process, while the obtained high value of 1/m indicates high initial rate of Magenta dye degradation.   Conclusion Due to the high homogeneous Fenton efficiency in our previous work a physico-chemical characterization of treated printing effluent was investigated. Conductivity and biological oxygen demand increasment was established, which together with the obtained mineralization degree indicated the formation of numerous low molecular weight fragments during the homogeneous Fenton process. However, the isolated by-products did not contribute to the toxicity increase, confirming that the treated printing effluent is nontoxic. Behnajady-Modirshahla-Ghanbary, as most appropriate kinetic model, indicated high initial rate and oxidation capacity of Magenta dye degradation during the homogeneous Fenton treatment.     25th International Symposium on Analytical and Environmental Problems 145 Acknowledgements The authors acknowledge the financial support of the Ministry of Education, Science and Technological Development of the Republic of Serbia within the Projects No. TR 34014 and III43005.  References [1] S. Karimifard, M. Moghaddam, Sci. Total. Environ. 640-641 (2018) 772. [2] V. Kecić, M. Prica, Đ. Kerkez, M. Bečelić-Tomin, A. Kulić, A. Leovac Maćerak, B. Dalmacija (2018) 13th International Scientific Conference “Flexible Technologies“ - MMA, 331. [3] Water quality - Determination of the chemical oxygen demand SRPS ISO 6060: 1994.  [4] Water quality - Guidelines for the determination of total organic carbon (TOC) SRPS ISO 8245:2007. [5] Water quality - Determination of anionic surfactants by measurement of the methylene blue index MBAS (ISO 7875-1:1984 modified) SRPS EN 903:2009. [6] Water quality - Determination of chloride - Silver nitrate titration with chromate indicator (Mors method) - Amendment 1 SRPS ISO 9297/1:2007 [7] Water quality - Determination of phosphorus - Ammonium molybdate spectrometric method (ISO 6878:2004) SRPS EN ISO 6878:2008. [8] Water quality - Determination of the inhibitory effect of water samples on the light emission of vibrio fischeri (luminescent bacteria test) - part 3, ISO 11348-3:2009 [9] T. Liu, H. You, React. Kinet. Mech. Cat. 109 (2013) 233. [10] M. El-Haddad, A. Regti, R. Laamari, R. Mamouni, N. Saffaj, Journal of Materials and Environmental Science 5 (2014) 667. [11] A. Hassan, M. Rahman, G. Chattopadhay, R. Naidu Environmental Technology and  Innovation 15 (2019) 100380. [12] M. Behnajady, N. Modirshahla, F. Ghanbary, J. Hazard. Mater. 148 (2007) 98 [13] N. Ertugay, F. Acar, Arab. J. Chem. 10 (2017) S1158.   

Characterization and kinetic study of magenta printing effluent after homogeneous fenton treatment

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Characterization and kinetic study of magenta printing effluent after homogeneous fenton treatment

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