Acute toxicity test under optimal conditions of two commercial reactive dyes using the Fenton-like process: Assessment of process factors by Box– Behnken design Natwat Srikhao Khon Kaen University Arthit Neramittagapong ( [email protected] ) Khon Kaen University https://orcid.org/0000-0002-7420-2196 Pongsert Sriprom King Mongkut's Institute of Technology Ladkrabang Sutasinee Neramittagapong Khon Kaen University Somnuk Theerakulpisut Khon Kaen University Nurak Grisdanurak Thammasat University Research Article Keywords: freshwater fairy shrimps, immobilization, iron powder, commercial reactive dye, decolorization, response surface methodology Posted Date: February 15th, 2021 DOI: https://doi.org/10.21203/rs.3.rs-164955/v1 License: This work is licensed under a Creative Commons Attribution 4.0 International License. Read Full License 1 1 Acute toxicity test under optimal conditions of two commercial reactive dyes using the Fenton-like process: 2 Assessment of process factors by Box–Behnken design 3 Natwat Srikhao1, 2, Arthit Neramittagapong1, 2,*, Pongsert Sriprom3, 4 Sutasinee Neramittagapong1, 2, Somnuk Theerakulpisut4, Nurak Grisdanurak5 5 1 Department of Chemical Engineering, Faculty of Engineering, Khon Kaen University, 6 Khon Kaen 40002, Thailand 7 2 Research Center for Environmental and Hazardous Substance Management (EHSM), 8 Khon Kaen University, Khon Kaen 40002, Thailand 9 3 Program of Food Processing Engineering, Faculty of Agro-Industry, 10 King Mongkut's Institute of Technology Ladkrabang, Ladkrabang, Bangkok 10520, Thailand 11 4 Energy Management and Conservation Office, Faculty of Engineering, Khon Kaen University, Khon Kaen, 40002, 12 Thailand 13 5 Department of Chemical Engineering, Faculty of Engineering, Thammasat University, Pathumthani, 12000, 14 Thailand 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 2 37 Abstract 38 39 Reactive dye has generally been used in woven cotton fabric dyeing industries. Some treatments of several 40 reactive dyes may produce more toxicity than the original dyes. The objectives of this study were to find the optimal 41 condition on dye degradation efficiency of commercial reactive red dye 36 (DR36) and reactive violet dye 30 (DV30) 42 using Fenton-like reaction, and to determine acute toxicity by static bioassay method under the optimal condition. The 43 experiment was designed by Box Behnken Design (BBD), in which an initial pH, catalyst dosage and initial 44 concentration of H2O2 were considered as independent variables. The results showed that only an initial pH solution 45 was the principal parameter which influenced decolorization of the reactive dyes. Other factors were much less 46 significant. The optimal conditions were found to be given by pH 3, 1 g/L of catalyst dosage, 27.63 mM of 47 concentration of H2O2 for DR36, and pH 3, 1.35 g/L of catalyst dosage, 45 mM of concentration of H2O2 for DV30. 48 Ninety percent of both decolorization were achieved in 30 min. Acute toxicity tests of the treated solutions using 49 freshwater fairy shrimps (Streptocephalus sirindhornae) revealed that the shrimps survived longer than 24 h, 50 indicating that the treated solutions were not acutely toxic. The average leaked iron, ADMI value and total organic 51 carbon were found to be less than 10 ppm, 5 ADMI and 9.17 ppm respectively, in the treated samples. This research 52 demonstrated an efficient method for decolorization of the reactive dyes with low acute toxicity. 53 54 Keywords: freshwater fairy shrimps, immobilization, iron powder, commercial reactive dye, decolorization, 55 response surface methodology 56 57 *Corresponding author E-mail: [email protected] (Arthit Neramittagapong ) 58 59 60 61 62 63 64 65 66 67 68 69 3 70 71 1.Introduction 72 Global textile industries have grown unstoppably for several decades, more over 700,000 ton of about 10,000 73 types of dyes and pigments were annually produced (Lyu et al. 2016; Holkar et al. 2016). Consequently, dye, especially 74 reactive dye, has become an important feedstock used in the industry. Since dye cannot be consumed totally in the 75 dyeing process, the unreacted dye could remain in the wastewater discharge, causing the wastewater to have 76 unpleasant appearance and toxicity. In Thailand it has been regulated that wastewater discharge should contain dye 77 concentration less than 300 ppm (Nidheesh et al. 2018) and/or the color of the wastewater should be less than 300 78 ADMI unit. Some reactive dyes were also declared as high toxins promoting carcinogenesis and mutagenesis (Nasuha 79 et al. 2016; Mahmood Reza Sohrabi et al. 2016). 80 To meet all the requirements of wastewater, several techniques have been used to reduce dye concentration 81 before the wastewater can be discharged. Advanced oxidation processes (AOP) are some promising methods used for 82 the purpose. These processes have been classified as photo-catalytic (Ayyob et al. 2020), ozonation (Powar et al. 83 2020), and Fenton reaction (Ertugay & Acar 2017). Among the AOPs, the Fenton reaction can extensively be used to 84 decompose hard biodegradable organics, including different dyes (Nasuha et al. 2016; Youssef et al. 2016), and textile 85 discharge (Ghanbari et al. 2014; Punzi et al. 2015). The reaction involves a reaction of ferrous ion with H2O2 to 86 produce OH• free radicals having extremely strong oxidation capacity, especially in narrow pH range of 2.8-3.0 87 (Ghanbari et al. 2014; Glugoski et al. 2017). The narrow pH range makes the Fenton reaction difficult to implment 88 (Wang et al. 2017). The heterogeneous Fenton-like catalytic technique has therefore been used more widely, as has 89 been reported on laterite soil (Khataee et al. 2015), red mud (Dias et al. 2016), montmorillonite clay (Fida et al. 2017), 90 zeolite (Rache et al. 2014) and zero valent iron nanoparticles (Vilardi et al. 2018). 91 Reactive dye such as DR36 and DV30 possesses prominent properties for their stabilities (Malade & 92 Deshannavar 2018) and high level of washing fastness (Nallathambi & Venkateshwarapuram Rengaswami 2017). 93 Nasuha et al. (2016) have studied decolorization of reactive black 5 using Fenton-like. Initial dye concentration, 94 hydrogen peroxide concentration, initial pH of a solution and amount of initial catalyst were selected as the main 95 factors for studying this reaction. Khataee et al. (2016) have also studied the effects of operating parameters of the 96 reaction such as catalyst dosages, [pH], [H2O2] on their decolorization of Reactive Orange 29 dye. However, the 4 97 decolorization of these reactive dyes have been studied by considering one factor at a time (OFAT). Interaction effects 98 of the parameters were not studied during the tests. 99 Statistical experimental design could be a better approach in multi-factor study. A systematic study using 100 response surface methodology (RSM), like central composite design (CCD) and Box Behnken Design (BBD), could 101 be used to set up and analyze the experimental data. Some of the advantages of the RMS include its ability to explain 102 both individual and interaction effects, and optimizing decolorization condition. In addition, it’s has successfully been 103 applied to various oxidation processes to optimize the experimental design condition (Fu et al. 2009; Berkani et al. 104 2020). 105 In this study, the decolorization of DR36 and DV40 dye was implemented by BBD under three factors 106 simultaneously, including pH, catalyst loading, and amount of H2O2. The study was carried out using iron powder in 107 a Fenton-like reaction. The experiment was set up in a range of pH 3-7, Catalyst 0.01-1.5 g/L, and H2O2 0.5-100 mM. 108 The optimum condition and the most influential factor(s) in decolorization of the reactive dyes were the objective of 109 this study. The water after the treatment was also tested for acute toxicity by using fairy shrimps (Streptocephalus 110 sirindhornae). 111 112 2.Materials and methods 113 2.1 Materials 114 Reactive red dye 36 (DR36) and violet dye 30 (DV30) (without heavy metal, Dylon, England) used in this 115 study were purchased in Thailand. The Fenton-like experiment were carried out using commercial iron-powder grade 116 (99.64% Gammaco, Thailand). H2O2 30% (QRëC, New Zealand). NaOH (98%wt Ajax Finechem Pty Ltd, Auckland, 117 New Zealand) and H2SO4 (96%wt RCI Labscan Limited, Thailand) were used to adjust the solution pH to the desired 118 levels. Ethanol (99.8% Analar NORMAPUR ® ACS, Reag.Ph.Eur. , France) was used to wash the catalyst. Nylon 119 filter membrane (Syring filter 0.45 Micron CNW, China) was used to filter the sample solution before determining 120 the color values using UV-Vis spectrophotometer (SPECORD,Analytik Jena, Germany). All solutions were prepared 121 with deionized water (DI water). 122 123 2.2 Experimental 5 124 Iron-powder was sieved to the size range of 100-500 mesh. It was washed by Deionized water and ethanol, 125 and then dried at 80oC for 1 hour. The obtained material was immediately used right after the preparation. Box– 126 Behnken design (Software Minitab 16) was used to randomize the experimental values of the three factors at three 127 levels as shown in Table 1. The studied factors included initial pH, catalyst dosage, and initial concentration of H2O2. 128 The experiments were performed in a batch-wise system of 600 mL container, under room temperature. The 129 decolorization of reactive dye (300 ppm) was carried out using different initial concentrations of H2O2 (0.5-100 mM), 130 the catalyst dosage (0.01-1.5 g/L) and pH (3-7). One molar of H2SO4 or NaOH solution was used to adjust the solution 131 pH. 132 During the test, the remaining concentration of the reactive dye in the solution was withdrawn 30 minutes 133 after the beginning of the experiment, and analyzed for the percentage of decolorization efficiency (DE%) and the 134 American Dye Manufacturers Institute (ADMI) value by UV-Vis spectrophotometer.