Accepted Manuscript

Title: Equilibrium and Kinetic Models on the Adsorption of

Reactive Black 5 from Aqueous Solution using Eichhornia
Crassipes/Chitosan Composite

Author: Manal M. El-Zawahry Fatma Abdelghaffar Rehab A.

Abdelghaffar Ahmed G. Hassabo

PII: S0144-8617(15)00936-4
DOI: http://dx.doi.org/doi:10.1016/j.carbpol.2015.09.071
Reference: CARP 10373

To appear in:

Received date: 17-6-2015

Revised date: 6-9-2015
Accepted date: 22-9-2015

Please cite this article as: El-Zawahry, M. M., Abdelghaffar, F., Abdelghaffar, R. A., and
Hassabo, A. G.,Equilibrium and Kinetic Models on the Adsorption of Reactive Black 5
from Aqueous Solution using Eichhornia Crassipes/Chitosan Composite, Carbohydrate
Polymers (2015), http://dx.doi.org/10.1016/j.carbpol.2015.09.071

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 1 Highlights
2 New natural biopolymer composite was prepared using Eichhornia Crassipes and chitosan
3 Surface characterization of Eichhornia crassipes/chitosan composite was examined
4 Sorption experiments were carried out as a function of pH, dye conc. and time
5 EC/Cs have high ability to remove Reactive Black 5 from its dyebath effluent
6
7
8 Equilibrium and Kinetic Models on the Adsorption of Reactive Black 5 from Aqueous Solution
9 using Eichhornia Crassipes/Chitosan Composite

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10

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11 Manal M. El-Zawahrya, Fatma Abdelghaffara, Rehab A. Abdelghaffara, Ahmed G.
12 Hassabob*aga.hassabo@hotmail.com
13

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14 National Research Centre (Scopus afflitiation ID 60014618), Textile Research Division, Dyeing, Printing and
15 Textile Auxilaries Department, El-Behouth St. (former El-Tahrir str.), Dokki, P.O. 12622, Giza, Egypt
b
16 National Research Centre (Scopus afflitiation ID 60014618), Textile Research Division, Pre-treatment and Finishing

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17 of Cellulosic Fibers Department, El-Behouth St. (former El-Tahrir str.), Dokki, P.O. 12622, Giza, Egypt
18
19 Abstract

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20 New natural biopolymer composite was prepared using extracted cellulose from an
21 environmentally problematic water hyacinth Eichhornia Crassipes (EC). The extracted cellulose
22 was functionalized by chitosan and TiO2 Nanoparticles to form EC/Chitosan (EC/Cs) composite
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23 network. Surface characterization of EC/Cs natural biopolymer composite was examined by
24 spectrum analysis FT-IR, specific surface area, micropore volume, pore width and SEM.
Furthermore, the sorption experiments were carried out as a function of pH, various initial dye
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25
26 concentration and contact time. Experiment results showed that the EC/Cs composite have high
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27 ability to remove C.I. Reactive Black 5 from its dye-bath effluent.

28 The equilibrium sorption evaluation of RB5 conformed and fitted well to Langmuir
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29 adsorption isotherm models and the maximum sorption capacity was 0.606 mg/g. The kinetic
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30 adsorption models followed pseudo- second order model and the dye intra-particle diffusion may
31 suggesting a chemical reaction mechanism. Further, it was obvious from the investigation that
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32 this composite could be applied as a promising low cost adsorbent for anionic dye removal from
33 aqueous solutions.
34

35 Keywords
36 Eichhornia Crassipes, chitosan, biopolymer composite, Reactive Black 5, adsorption isotherm,
37 kinetics
38

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39 1. Introduction
40 Various polutants can reach the environment through the discharge of industrial and
41 domestic effluents. In textile industry, for example, during the dyeing process 10–15% of textile
42 colorants are released to the aquatic environment, and in case of direct and reactive dyes, almost
43 30% can be found in the final effluent (Al-Degs, El-Barghouthi, El-Sheikh & Walker, 2008;
44 Horvat et al., 2012).

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45 Reactive dyes are commonly used in textile industries because of simple dyeing procedure
46 and covalent binding with cellulose fibers. However, a higher percentage of such dyes during the

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47 dyeing process can no longer react with the cellulose fiber because of the hydrolysis side reaction.
48 Thus, approximately 20% of the initial dye concentration is present in the reactive dye bath,

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49 giving rise to a highly colored effluent (Al-Degs, El-Barghouthi, El-Sheikh & Walker, 2008;
50 Vijayaraghavan, Won & Yun, 2009). Many reactive dyes are toxic to biotic communities in
aquatic ecosystem and the environment (Kadirvelu, Faur-Brasquet & Cloirec, 2000). The

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51
52 presence of such dyes in water bodies may be mutagenic and carcinogenic and can cause severe
53 damage to the liver, digestive and the central nervous system of human beings and affect
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54 agricultural cultivation and underground water quality (Nasr, Abo El-Ola, Ramadan &
55 Hashem, 2006; Sivaraj, Namasivayam & Kadirvelu, 2001).
56 Therefore, it is necessity to treat reactive dye effluents before their discharge into
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57 ecosystem. Numerous physical, chemical, and biological techniques have been developed for the
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58 removal of reactive dyes from effluents. From which, adsorption method has been proven to be an
59 interesting and effective technique for the treatment of dye bearing waste waters with no
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60 unwanted by-products and of its simple design and low initial investment cost. Activated carbon
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61 is most widely used because of its high efficiency. However, in this context, its high cost and
62 difficulty to regenerate after use affect its application in industry.(Balcioglu, Arslan & Sacan,
63 2001)
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64 In recent years, several authors have reported various kinds of low cost agricultural based
65 materials as dye adsorbents, for example, straw, bacteria, phoenix leaf powder, rice husk, chitosan
66 (Cs), peanut husk, jackfruit leaf powder, grape stalk waste, and so on (Nilsson, Nordlinder,
67 Wass, Meding & Belin, 1993; Satapanajaru, Chompuchan, Suntornchot &
68 Pengthamkeerati, 2011). However, the main problem associated with those bio adsorbents is
69 their non-abundant availability in the global market; this eventually makes them incapable of
70 meeting the huge commercial demand (Nilsson, Nordlinder, Wass, Meding & Belin, 1993).
71 Water hyacinth plant, Eichhornia crassipes (EC) is a free-floating aquatic plant, which is
72 considered as the worst aquatic plant in Egypt since causes a major problem economically in open

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 73 water bodies as it negatively affects fishers, prevent water traffic, irrigation, power generation,
74 and boating. EC has high cellulose content (~ 40 – 60% α cellulose) (Mochochoko, Oluwafemi,
75 Jumbam & Songca, 2013) which has the potential of being used as alternative sorbent for the
76 removal of metals and dyes from waste water. (Miretzky & Muñoz, 2011; Wanyonyi, Onyari &
77 Shiundu, 2013) various chemical modifications such as esterification, etherification, amination
78 and copolymerization were employed to improve the sorption capacity of raw EC dead biomass

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79 (El-Zawahry, 1998; El-Zawahry & Kamel, 2004).

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80 The use of cellulose fiber wastes in biopolymer composite materials and its application in

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81 material science and environmental sciences have been reported. (Hassabo, Salama, Mohamed
82 & Popescu, 2015) Recently, more research activities have been focused on the synthetic

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83 polymers and biopolymers composites and their sorption capacities have been investigated for
84 the removal of reactive dyes from their aqueous solution e.g. sodium alginate/isopropyl
85 acrylamide, polyaniline/chitosan, bacterial extracellular polysaccharides /polyaniline and

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86 starch/polyaniline have also reported. (Dhanapal & Subramanian, 2014; Janaki et al., 2012)
87 Furthermore, the incorporation of a small amount of inorganic nanoparticles can improve the
88 performance of the dispersability, hydrophilicity, antimicrobial and catalytic properties of a
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89 biopolymer composite or matrix (El-Zawahry, Hakeim, Abdelghaffar & El-Hawary, 2014).
90 The ultimate goal of this work was to design a new kind of biopolymer composite network
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91 based on using cellulose fibers extracted from an aquatic weed, water hyacinth EC, TiO2 NPs and
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92 natural biopolymer chitosan. During this study RB5 dye was chosen as a dye effluent model. The
93 physico-chemical and sorption properties of EC/Cs composite network were characterized using
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94 BET, SEM and FT-IR. The factors affecting the adsorption properties or removal of RB5 dye
95 were studied by varying the concentration of dye, initial pH and contact time. The adsorption
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96 isotherms and kinetic models of the removal process will also be studied to identify the possible
97 mechanism to removal RB5 from textile effluent dye-bath.
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98

99 2. EXPERIMENTAL
100 Materials and methods
101 Biosorbent
102 The aquatic weed plant Eichhornia Crassipes (EC) was collected from fresh water canals at El-
103 Marg region, Delta, Egypt). The plant stems and leafs were washed well with tap water to
104 eliminate the sediments and kept on a filter paper to reduce the water content. Then, it was dried
105 for one week under normal sunlight conditions. Finally, the EC stems and leafs were cut into
106 small pieces, milled and further ground to powder form in a mixture.

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107

108 Dyestuffs and Chemicals

109 The dye used in this study is Reactive Black 5 (RB5). This dye was kindly supplied, by
110 Sigma-Aldrich USA (molecular weight = 991.82 g/mol, C.I. no. = 306452, λmax = 597 nm) and
111 it is used as received and the chemical structure was shown in
112 Fig. 1. Titanium dioxide (TiO2) NPs has a particle size less than 100 nm and high

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113 molecular weight chitosan was supplied by Sigma–Aldrich Chem., Germany. The other chemical

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114 reagents employed in this study were: sodium hydroxide, hydrogen peroxide (50%), glacial acetic

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115 acid and they are of a laboratory grade reagents.
116

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118 2.1.1. Preparation of cellulose fibers
119 The ground fibers of EC was treated with a 2% (w/w) sodium hydroxide solution at

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120 100°C for 4 h under mechanical stirring, washed several times with distilled water until the alkali
121 was completely removed and finally dried at 60°C for 12 h in an air-circulating oven (Santos,
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122 Flauzino Neto, Silvério, Martins, Dantas & Pasquini, 2013). After this treatment, the material
123 was bleached with a solution of certain amount of H2O2 (5g/L of 45% H2O2) and sodium silicate
124 (3g/l) at pH=10.5 using aqueous sodium hydroxide solution with liquor ratio 1:20 at 95°C for 30
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125 min. Finally the bleached cellulosic fibers was washed several times with distilled water until the
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126 pH of the material became neutral and subsequently dried at 60°C for 12 h in an air-circulating
127 oven or room temperature then fine ground well (Abou-Okeil, El-Shafie & El-Zawahry, 2010;
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128 El-Zawahry, Hakeim, Abdelghaffar & El-Hawary, 2014).

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129

130 2.1.2. Preparation of EC/Cs natural network composite

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131 The natural network composite (EC/Cs) was prepared by dissolving 1g of chitosan (Cs) in
132 one liter of 3% glacial acetic acid solution with good stirring and leave it overnight at room
133 temperature. Then, 10 g of purified EC fibers was immersed into one litter of an acetylated
134 chitosan solution and sonicated with ultrasonic homogenizer (Sonic &Materials, INC, model:
135 VCX750, volts: 230 VA 50/60 HZNOM, USA) for 15 min. The TiO2 NPs (1g/l) suspension were
136 added gradually into EC/Cs solution, subsequent sonicated with ultrasonic homogenizer for
137 further 15 min. to allow the homogeneous dispersion of TiO2 NPs. The EC-chitosan-TiO2 solution
138 was left for 15 min. at room temperature. Finally, the suspension was washed with deionized
139 water through four cycles of centrifugation (4000 rpm, for 30 min) to remove the unbound TiO2

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140 NPs and dried at 60°C for 12 hr. then milling well. The schematic diagram for the designing
141 EC/Cs natural network composite was shown in Figure 2.

142

143

144 2.1.3. Characterization of EC fibers and EC/Cs composite

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145 2.1.3.1. FT-IR analysis

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146 Fourier transform infrared (FT-IR) spectra was performed to investigate the functional
147 groups presenting in crude and purified EC fibers, Cs, TiO2 NPs and EC/Cs natural network

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148 composite using FT-IR spectroscopy. FT-IR spectra were recorded on a Nexus 670 FT-IR
149 Spectrometer, Nicolet Company, USA, using potassium bromide disks. A total of 32 scans for

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150 each sample were taken with a resolution of 4 cm−1, with a range of 4000–400 cm−1.
151 2.1.3.2. Surface characterization

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152 Analysis of the surface of purified EC fibers and EC/Cs natural network composite were
153 characterized by BET specific surface area, micro pore volume, pore size distributions, SEM,
contact angle measurement and the degree of swelling observation. The morphology of the
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154
155 surface was obtained by SEM Model Philips XL 30 with an EDX unit attached, with accelerating
156 voltage of 30 kV and magnification between 10X up to 400.000X all the samples were coated
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157 with gold before SEM testing. In addition, the specific surface area was determined by the
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158 nitrogen adsorption isotherm technique, with an automatic BET surface area analyzer (Model F-
159 Sorb 2400, Beijing Jinaipu Technical Apparatus Co., Ltd., China). The nitrogen adsorption was
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160 carried out at 77 k. The wettability of the crude, purified EC and EC/Cs composite was measured
161 with deionized water contact angle measurements using compact video microscope manufactured
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162 by SDL-UK). Deionized water was automatically dropped onto the composite according to
163 ASTM D724-99 standard test method for surface wettability of paper and ASTM D5946-96
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164 standard test method for corona-treated polymer films. On the other hand, the degree of swelling
165 of the crude, purified EC, EC grafted with chitosan and EC grafted with chitosan and loaded with
166 1 g/l TiO2 NPs (EC/Cs composite) was measured at room temperature as discussed elsewhere.
167 (Dhanapal & Subramanian, 2014) the degree of swelling for each sample at equilibrium was
168 calculated by taking an average of three absorption to using the following equation:

169 Swelling % =
170 where Ws and Wd are the weight of the swollen composite or fibers and the dry composite
171 of fiber respectively.

172

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173 2.1.4. Adsorption and Isothermal Studies
174 Five known concentrations for each RB5 were prepared and measured using 5 cm quartz
175 cells housed in a UV/visible spectrophotometer (UV- 1601 Shimadzu, Japan) at λmax= 597 nm to
176 make the calibration standard curve to allows us to convert the absorbance measured into
177 concentration in order to monitoring the amount of RB5 adsorbed.
178 The batch adsorption experiments were performed in Erlenmeyer flasks containing 100 ml

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179 of the dye solution with concentration (20-300 mg/l) where 2 g of the natural network composite
180 was added. The pH of the solutions was found to be in the range of 2-10 using acetic acid or

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181 NaOH. The flasks were subjected to shaking at a constant speed of 400 rpm at 30°C on a
182 horizontal shaker. The Erlenmeyer flasks were subsequently agitated for 3 h to achieve

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183 equilibrium. The concentration of the RB5 in the solution after equilibrium adsorption was
184 measured using a UV/visible spectrophotometer (UV- 1601 Shimadzu, Japan) at λmax= 597 nm,
185 and all the adsorption experiments were performed in duplicate, and the mean values were
reported.

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187 For kinetic studies, after the treatment, sampling was done at different time (10–120 min).
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188 5 ml of the sampled aqueous phase was measured for the residual concentration of RB5 using a
189 UV-Vis spectrophotometer, and then put back into the treatment solution for keeping the
190 concentration constant.
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191 For isotherm studies, 100 ml of the solutions of various RB5 concentrations (20 – 300
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192 mg/l) were prepared in separate 250 ml conical flasks. 1g of composite was transferred into each
193 of the conical flasks. After 30 min, the solution was measured then the absorbance was converted
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194 to concentration. Duplicate experiments were performed in parallel to check the results.
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195

196 Error analysis

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197 Because of the inherent bias resulting from the linearization of the isotherm
198 and kinetic models, four different error functions of the non-linear regression basin
199 were employed as criteria for the quality of fitting. (Sahmoune & Louhab, 2010;
200 Sahmoune, Louhab & Boukhiar, 2009; Wasewar, Atif, Prasad & Mishra, 2008)
201

202 The root mean square error (RMSE)

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203 The root mean square test (RMSE) has been used by a number of researchers
204 in the field to test the adequacy and accuracy of the model fit with the experimental
205 data:

206 RMSE =

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207 where qi is the experimental sorption capacity from the batch experiment i,
208 qi.e is the sorption capacity estimated from the sorption model for corresponding qi

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209 and n is the number of observations in the batch experimental.

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210

211 The chi-squared test (X2)

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212 The chi-squared test (X2) statistic is basically the sum of the squares of the
213 differences between the experimental data obtained by calculating from models,
with each squared difference divided by the corresponding data obtained by
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215 calculating from models. The chi-squared test has some similarity with the root
216 mean square error and is given as:
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217 X2 =
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218
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219 The sum of absolute errors (SAE)

220 The sum of absolute errors (SAE) is given as:
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221 SAE =
222 The isotherm parameters determined by this method provide a better fit as the
223 magnitude of the errors increase, biasing the fit towards the high concentration data.
224

225 The average relative error (ARE)

226 The average relative error (ARE) is defined as:

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227 ARE =
228 This error function attempts to minimize the fractional error distribution
229 across the entire concentration range.

230

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230 3. RESULTS AND DISCUSSION
231 3.1. Preparation of EC/Cs biopolymer composite
232 The natural biopolymer composite was firstly formed by functionalization of the cellulosic
233 fibers extracted from EC water hyacinth with Cs. This reaction is achieved by the electrostatic
234 interaction between the negative charged –OH groups of cellulose fibers and the positive charge –
NH+3 anion of Cs under strong acidic condition. Moreover, stirring the cellulose fibers treated

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236 with chitosan dispersion in the presence of to 1% TiO2 for 15 min to form an effective chelating
237 agents and multifunctional EC/Cs composite. It has confirmed that TiO2 NPs act as chelating

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238 agents and form a network (mats), which can lead to a remarkable increase in the number of
239 active sites associated with an improvement in hydrophilicity and polydispersability of the

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240 cellulose fibers, as given by contact angle and swelling (%) measurements.
241 Additionally, incorporation of a small amount (1g/l) TiO2 NPs was added the grafted EC

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242 with Cs can improve the overall performance of biopolymers (EC and Cs) e.g. hydrophilicity and
243 diffusion of the polymeric composite. The role of TiO2 may be attributed to form or produce
244 complexes with the nitrogen atom of the excess unreacted amino groups of Cs with EC and form
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245 a thin layer of chitosan - TiO2 over the EC surface by intermolecular hydrogen bonds. TiO2 NPs
246 react with double soul reaction electrostatic force between excess amino groups of Cs and TiO2
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247 and as chelating agent by the hydrogen bonds of OH groups of Cs.
248
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249 3.2. Characterization of EC/Cs composite

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250 3.2.1. FT-IR spectra

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251 The FT-IR spectrum of crude EC fiber, purified EC fibers, Cs, TiO2 NPs and EC/Cs
252 natural composite were shown in Figure 3. It was obvious from Figure 3 that crude EC fiber
253 shown three bands around 3433.64, 2924.52 – 2857.02 and 846.6 – 1045.23 cm-1. These bands
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254 may be assigned to the stretching vibrations of O-H, C-H asymmetric and symmetric stretching of
255 methylene and methyl group and C-O-C group respectively. Also, a small peak at 1735 cm-1 was
256 observed in the spectrum due to the presence of either acetyl and uronic ester linkage of
257 carboxylic group of ferulic and p-comumeric acid of lignin and/or hemicelluloses. Similarly, in
258 Figure 3 the spectrum of purified E.C. also exhibits these three bands at 3441.35, 2926.45 and
259 769.46 – 1005.7 cm-1 which may be assigned to the stretching vibration of –OH, -CH and C-O-C
260 group. Although, the peak appeared at 1735 cm-1 in crude EC was disappeared in the bleached EC
261 after the purification process. Both, the crude and purified EC fibers have a peak at 1642.09 cm-1
262 representing O-H bending vibration of absorbed water and the intensity of this peak was

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263 decreased in purified E.C. than crude EC fiber due to the removing of hemicelluloses
264 (Mochochoko, Oluwafemi, Jumbam & Songca, 2013). The FT-IR spectrum of Cs powder was
265 shown in Figure 3, in which a characteristic peaks appears as a broad band around 3200 – 3650
266 cm-1 may be assigned to O-H and N-H stretching vibrations, 2923.56 cm-1 (C-H stretching
267 vibration), 1645.95 cm-1 (C=O, amide 1), 1546.63 cm-1 (N-H stretching deformation), 1384.64
268 cm-1 (CH3 symmetrical deformation) and 1160.94 – 1029.8 (ether bonding) (Tran, Duri, Delneri

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269 & Franko, 2013). In Figure 3 the band appear at 653.75 cm-1 was characteristic to titanium oxide

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270 NPs and refer to the stretching vibration of Ti-O-Ti in which the bending vibration of coordinated
271 H2O and Ti-OH creates the absorbance at 1642.09 cm-1 and the surface absorbance of hydroxyl

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272 groups are at 3427.85 cm-1. The FT-IR bands for the EC/Cs network composite was shown in
273 Figure 3 and it was possible from it to confirm the preparation of the composite. Bands of OH

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274 stretching (3650 – 3200, 1200 – 1000 cm-1) and CH stretching (2900 – 2850, 1500 – 1300 cm-1),
275 which could be attributed to the presence of both purified EC and chitosan natural polymers in the

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276 same spectra of Figure 3. At the same time, the broad absorption peaks corresponded to N-H
277 stretching of amide and carbonyl group of Cs (1539.88, 1642.09 cm-1) were observed in the
278 spectra of the composite, and this result may be due to the overlapping or coincident of both
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279 spectrum of EC and Cs in the composite which suggests that the Cs was more dispersed and
280 absorbed into the cellulose extracted from EC (Tran, Duri, Delneri & Franko, 2013).
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281
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282
283

284 3.2.2. Surface characteristics analysis

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285 The specific surface area of the natural biopolymer composite increased significantly than
286 the purified EC from 132.95 m2/g to 172.49 m2/g. This result may be attributed to the hydrophilic
287 coating of Cs polymer onto the surface of EC. Moreover, Cs has a good dispersant for TiO2 NPs,
288 which possesses a smaller particle size and uniform distribution associated with a large specific
289 area offering a network EC/Cs composite with a remarkable increase in the number of active sites
290 and form a multifunctional natural biopolymer composite. This was estimated by enhancing the

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291 dispersability and dye adsorption capacity. This result is confirmed by increasing the micropore

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292 volume from 0.0774 cm3/g in purified EC to 0.0913 cm3/g in EC/Cs natural network composite.
293 Also, the results of the SEM micrographs for the surface morphology of the crude, purified and

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294 natural biopolymer composite (EC/Cs) were observed as shown in Figure 4. The SEM
295 micrographs reveals that, the presence of Cs and TiO2 NPs in the final composite products,

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296 creates a rough surface associated with porous structure, indicating that the porous adsorption are
297 available and RB5 sorption mechanism occurs.

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298 The contact angle measurement provide a simply and convenient way to evaluate the
299 hydrophilicity of crude EC, purified EC and EC/Cs composite surface as shown in Figure 5. The
300 figure indicated that, there is no contact angle was observed for the crude EC, purified EC and
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301 EC/Cs composite i.e. zero contact angle representing complete wetting. However, the water
302 droplet caused swelling of the surface of the fibers and composite following the order: crude EC <
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303 purified EC < EC/Cs composite. The water droplet of EC grafted with Cs was absorbed in 1.3
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304 min. and was obviously higher than that of EC/Cs composite in which water droplet was absorbed
305 in 30 sec. with swelling on upper surface. This result may be attributed to the incorporation of
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306 TiO2 NPs into EC grafted with Cs via solution produced EC/Cs composite network and provide
307 more active sites associated with an improvement in the hydrophilicity of the cellulosic fibers of
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308 EC. It was also observed that the swelling % at equilibrium increased from crude EC (139.38 %)
309 to purified EC (148.22 %) to EC grafted Cs (265.50 %) to EC/Cs composite (435.04 %)
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310 respectively. These values indicates that incorporation of TiO2NPs in EC/Cs composite provide a
311 number of active sites associated with an improvement in the polydipersability of the cellulose
312 fibers.
313

314

315

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320

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322 3.3. Adsorption Study

323 3.3.1. Effect of pH on dye adsorption
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324 The effect of pH of the medium upon the uptake of RB5 dye by 1g/100 ml EC/Cs
325 composite using an initial dye concentration 40 mg/l is illustrated in Figure 6A. It is seen that the
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326 maximum uptake value (95%) was obtained at pH 2.5 - 3. This result may be due to that the
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327 acidic medium causes the amine active site in EC/Cs composite to be more protonated, which in
328 turn results strong electrostatic interactions between the – SO3- groups of the dye molecules and
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329 amine groups of the composite as represented by the following mechanism.

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330

OH OH
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OH
EC/Cs NH2 EC/Cs
+
NH3

+
pH = 3 EC/Cs NH
+ +
H2O
RB5 (SO3Na)2 RB5 (SO3- )2 + 2Na+
331
332

333 On the other hand, decrease in the dye uptake over the pH range 6 – 8 (74.5 – 72 %)
334 indicate that the electrostatic mechanism was not only the sole mechanism for the dye adsorption,

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335 but also the EC/Cs composite could interact with RB5 through hydrogen bonding. Increasing the
336 pH value more than 8 causes a sharp decrease in the uptake (55 – 24%). This observation may be
337 attributed to the decrease in dye dissociation, which leads to a lower concentration of the dye
338 species available to interact with the EC/Cs composite active sites. In addition, this behavior can
339 be explained by the lower extent of protonation of amino groups at higher pH (8 – 10).
340 Dye uptake was calculated from the difference between the dye concentrations in the

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341 supernatant using the following equation:

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342 Q= V(Co − Cf )/ M
343

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344 where Q is the dye uptake (mg/g), Co and Cf are the initial and final dye concentrations in
345 the solution (mg/l), respectively, V is the volume of the solution (L), and M is the mass of

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346 EC/Cs composite (g).
347

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348 3.3.2. Effects of the contact time on the adsorption of dye onto EC/Cs composite
349 Figure 6B shows the change in the uptake of RB5 by the EC/Cs as a function of time at
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350 initial dye concentration of 40 mg and pH 3. It was observed that, about 95% of the total uptake
351 of RB5 could be achieved within 60 min.

352
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 40

Concentration (mg (Dye) /1g EC composite)

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30

25
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0 10 20 30 40 50 60 70 80 90 100 110 120 130
Time (min.)
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357
358 3.3.3. Kinetic Study
359 The kinetics of the adsorption processes provides useful information regarding the
360 efficiency of adsorption and feasibility of scale-up operations. The concentration time curves
361 (Figure 6) of the adsorption of RB5 on the surface of composite suggest that RB5 adsorbs on the
362 prepared composite very well, exhausting about 95% from dye bath effluent.

t
ip
363 Three kinetic models were tested to find out the appropriate expression for the adsorption
364 rate, viz.: the pseudo-first-order (Kannan & Sundaram, 2001), the pseudo-second-order model

cr
365 respectively (Ho, Wase & Forster, 1996) and Intra-particle diffusion model (Xu, Gao, Yue &
366 Zhong, 2010). The pseudo-first-order rate equation is given below:

us
dq
= k1 ( q e − q t ) n
367 dt

where q t is the amount of dye adsorbed (mg/g) at time t, qe is the maximum adsorption

an
368

369 capacity (mg/g), k is the rate constant (min) and n is the reaction order. On integration the linear
370 form can be written:
M
371 ln( q e − q t ) = ln( q e ) − k 1 t for n=1 (first order reaction)

372 The rate of second-order model depends on the amount of dye adsorbed on the surface of
d

373 adsorbent and the quantity adsorbed at equilibrium (Caparkaya & Cavas, 2008). After integration,
te

374 the model was written as:

1  1  1  1
=   +
qt  k 2 qe 2  t  qe
p

375
ce

376 Where qt is the amount of dye adsorbed (mg/g) at time t, qe is the maximum adsorption
377 capacity (mg/g) for second-order adsorption, and k2 is the second-order rate constant (g/mg.min).
378 Both of pseudo first and second order models above cannot be only used to identify the
Ac

379 diffusion mechanism, but the intra-particle diffusion model was also proposed. The initial rate of
380 intra-particle was calculated using the following equation (Xu, Gao, Yue & Zhong, 2010):
381 Qt = Kd t1/2 + C
382 where kd is the intra-particle rate constant (g/mg min−0.5), and it is a function of
383 equilibrium concentration in solid phase, Qt and the intra-particle diffusion C can be determined.
384 From the above equations, the values of adsorption rate constant (k) for RB5 adsorption on
385 composite was determined. In addition, the values of other parameters and the correlation
386 coefficient was calculated for each plot. The value of reaction order was chosen for which the
387 best linear correlation is achieved (the highest value for R2). The corresponding values of rate-

16 Page 16 of 26
388 constant (k), and correlation coefficients R12 are given in Table 1. The results in Table 1 indicate
389 that the best fit is given by second-order kinetics model for the data of adsorption of RB5 by
390 EC/Cs composite in which the correlation coefficient (R2) was higher (0.9995) i.e. more linear
391 than that of the pseudo – first order model (0.9868). The second order kinetic model suggests also
392 that the mechanism of adsorption is a diffusional one via micropores (figures are omitted).
393 However, the plot of RB5 uptake Qt versus square root of time t1/2 do not pass through the

t
ip
394 origin in this study. This indicates that intraparticle diffusion in the sorption process not the only
395 rate limiting step but also other kinetic processes may be occurring and contribute with the

cr
396 sorption mechanism (Xu, Gao, Yue & Zhong, 2010).
397

us
398 Table 1: The values of the kinetic parameters as obtained from the experimental data

Pseudo first-order model Pseudo second-order model Intra-particle diffusion model

an
R2 0.9995 0. 9868 0.9341
K 0.102714 0.2871 0.1055
Qe 0.4598 0.4618
M
C -0.0746

399
d

400 3.3.4. Isothermal Studies

te

401 The maximum sorption capacities at different initial dye concentrations is measured using
402 uv-vis spectrophotometer, and the maximum sorption capacities values are represented as
p

403 adsorbed dye concentration (mg/g) or efficiency of dye adsorption (%) vs. different initial dye
ce

404 concentrations are shown in (Figure 7). It was obvious from the figure that, increasing the
405 amount of dye in the dye-bath from 2 – 30 mg/100 ml increased the maximum adsorbed dye
406 concentration with the same amount of EC/Cs composite (1g/100 ml). While calculation the
Ac

407 efficiency of dye adsorption (%) shows realizable reversible behavior, conclude that, efficiency of
408 dye adsorption is decreased as the amount of dye increased with different values until 10 mg/100
409 ml, then increasing of the dye amount cause decreasing of the dye efficiency.
410

411

17 Page 17 of 26
 t
ip
cr
us
412

an
M
d
p te
ce
Ac

413
414

415 The adsorbed dye concentration curve may be also used to describe the adsorption
416 isotherm, for modelling how EC/Cs composite interacts with RB5 dye (Hassabo, 2011; Hassabo,
417 Mendrek, Popescu, Keul & Möller, 2014).
418 Adsorption isotherms are described by many models, among most used for textile fibers
419 being those of Langmuir, Freundlich, BET and Dubinin – Radushkevich models (Hassabo, 2011;
420 Hassabo, Mendrek, Popescu, Keul & Möller, 2014).

18 Page 18 of 26
421 The Langmuir isotherm is widely used to describe single-solute systems (Wang, Boyjoo,
422 Choueib & Zhu, 2005). This isotherm assumes that intermolecular forces decrease rapidly with
423 distance and consequently it predicts monolayer coverage of the dye on the outer surface of the
424 EC/Cs composite. Further assumption is that adsorption occurs at specific homogeneous sites of
425 the EC/Cs composite surface and there is no significant interaction among the adsorbed species.
426 The Langmuir isotherm is given by the following equation:

t
qm Ce K L

ip
qe =
427
1 + Ce K L

cr
428 where qe is the equilibrium dye concentration on the EC/Cs composite (mg/g), Ce is the
429 equilibrium dye concentration in solution (mg/l), qm is the maximum capacity of the EC

us
430 composite (mg/g), and KL is the Langmuir adsorption constant (L/mg). Rearranging the terms in
431 the above equation, a linearization of the Langmuir isotherm can be written as shown in the next
432 equation. The plot of 1/qe versus 1/Ce gives a straight line with a slope of 1/qeKL and an intercept

an
433 of 1/qm.

1 1  1  1 
= +  
qe qm  qm K L  Ce 
M
434
435 Freundlich isotherm is good for describing heterogeneous systems (Wang, Boyjoo,
436 Choueib & Zhu, 2005). This empirical expression was used to study the adsorption of dye
d

437 compounds on EC/Cs composite surface. The Freundlich isotherm equation is given below:
te

q e = K F C e1 / n
438
p

439 where qe is the equilibrium dye concentration on the EC/Cs composite surface (mg/g), Ce
440 is the equilibrium dye concentration in solution (mg/l), KF is the Freundlich adsorption constant
ce

441 (L/mg), and n is the heterogeneity factor. The linear expression for the Freundlich isotherm is
442 shown in below equation. The plot of ln(qe) versus ln(Ce) gives a straight line with the slope of
Ac

443 1/n and an intercept of ln(KF).

1
ln qe = ln K F + ln Ce
444 n
445 The third isotherm model used in this study was Brunauer-Ernmett-Teller (BET) isotherm
446 model (DOULATI ARDEJANI, BADII, YOUSEFI LIMAEE, SHAFAEI & MIRHABIBI, 2008).
447 It was used for understanding the adsorption data and the liner form of this model written as:

Cf =
(K b − 1)(K bCmax Cs ) + K bCmax Ci
448
(Ci − Cs )(K b − 1)

19 Page 19 of 26
449 where Cf is the dye concentration adsorbed on the EC/Cs composite surface, Cs is the
450 concentration of dye in the treatment bath, Cmax is the maximum adsorption capacity of the EC/Cs
451 composite (mg/g), Ci is the saturation concentration of dye (mg/l), and Kb is the constant
452 describing the energy of interaction with the EC/Cs composite surface. The linear expression for
453 the Brunauer-Emmett-Teller isotherm (BET) is:

Cs 1  K −1  C s 
= +  b  

t
(Ci − Cs )C f K bCmax  K bCmax  Ci 

ip
454

455 The plot of (f C s (Ci − C s ) C f ) versus ( Cs Ci ) gives a straight line with the slope of

cr
456 ( (K b − 1) (K b × Cmax ) ) and the intercept of ( 1 (K b − 1) ).

Furthermore, the experimental data were fitted to Dubinin–Radushkevich (D–R) model in

us
457
458 order to determine if the adsorption occurred by a physical or chemical process. The D–R
459 equation is more general than the Langmuir model because it does not assume a homogeneous

an
460 surface or a constant sorption potential or absence of steric hindrance between sorbed and
461 incoming particles. The linear form of this model is represented by following equation

ln qe = ln qm − β ε 2
M
462
463 where qe (mmolg−1) is the amount of dye adsorbent per g of EC/Cs composite and qm
464 (mmolg−1) represents the maximum sorption capacity of the adsorbent, β (mol2.kJ−2) is a constant
d

465 related to sorption energy while ε is the Polanyi sorption potential calculated by the following
te

466 equation:
1
ε = RT ln (1 +
p

)
467
Ce
ce

468 where R is the gas constant 8.314 J.mol−1.K−1, T is the temperature in Kelvin and Ce (M)
469 is the dye equilibrium concentration. The Polanyi sorption approach assumes a fixed volume of
470 sorption space close to the sorbent surface and the existence of a sorption potential over these
Ac

471 spaces. The sorption space approximately a solid surface is characterized by a series of
472 equipotential surfaces having the same sorption potential. This sorption potential is independent
473 of the temperature but varies according to the nature of the sorbent and sorbate.
474 The values of β and qm were calculated from the slope and intercept of the plot ln qe vs ε2
475 (Table 2).The mean free energy of sorption E (kJ mol−1) required to transfer one mole of dye
476 from the infinity in the solution to the surface of EC/Cs composite can be determined by the
477 following equation:
1
−

478 E = (−2β ) 2

20 Page 20 of 26
479 All The parameters value resulted from curve fittings with the above four adsorption
480 isotherms are listed in Table 2. Dubinin–Radushkevich isotherm is generally applied to express
481 the adsorption mechanism with a Gaussian energy distribution onto a heterogeneous surface. The
482 approach was usually applied to distinguish the physical and chemical adsorption of RB5 dyeing
483 its aqueous solution with its mean free energy, E per molecule of adsorbate (for removing a
484 molecule from its location in the sorption space to the infinity). As the mean free energy, E=

t
485 10.78 KJ/mol indicating a exothermic and chemo-sorption process (Dada, Olalekan, Olatunya

ip
486 & DADA, 2012). As one may notice, Langmuir adsorption model fits better the experimental data
487 in which R2 = 0.9998 than the other models does (as evident from correlation coefficients R2). In

cr
488 addition, the fit to Langmuir model suggests that RB5 dye can adsorbs on active sites of the
489 EC/Cs composite and form a monolayer coverage. Furthermore, as n value from Freundlich

us
490 model > 1, so, it represents the favorable adsorption conditions (Hameed, Mahmoud & Ahmad,
491 2008).

an
492 From these results, it is difficult to select the best adsorption isotherm model. Therefore,
493 the correlation coefficient R2 and four different error functions were calculated to find out the
494 best isotherm model. By comparing the values, which they are listed in Table 2, it was found that
M
495 the Langmuir isotherm model fitted well to the observed data. In addition, the high value of R2
496 and low error function values for the Langmuir isotherm conclude that, the surface of the
d

497 adsorbent is made up of a homogenous adsorption area.

te

498

499 Table 2: Comparison between the parameters of adsorption isotherm models

p

Langmuir Freundlich BET Dubinin –

ce

model model model Radushkevich model

R2 0.9998 0.999 0.9916 0.9527
Cmax(mg dye/g) 0.60606 --- 0.592602 0.9887
K 12.3278 5.6663 6.497028 ---
Ac

n --- 1.052 --- ---

β --- --- --- -0.0043
E (KJ mol-1) --- --- --- 10.78
RMSE 0.319 0.417 0.335 0.746
X2 0.838 1.246 0.885 2.811
SAE 52.596 52.317 52.436 52.748
ARE 191.499 214.293 198.198 285.333
500

501 4. CONCLUSION
502 In this work, we are success to design a new kind of biopolymer EC/Cs composite
503 network based on cellulosic fibers extracted from an aquatic weed, water hyacinth Eichhornia

21 Page 21 of 26
504 crassipes, TiO2 NPs and natural biopolymer chitosan. The EC/Cs biopolymer composite was
505 characterized by FT-IR, SEM and surface area measurements. The surface area was calculated to
506 be 0.0913 cm3/g, which reflects the hydrophilic character of the prepared composite. Removal of
507 RB5 from aqueous solutions was studied using EC/Cs composite and the nature of interaction
508 between the dye anions and the EC/Cs composite was found to be dependent upon the pH of the
509 medium. The results showed that sorption process was carried out by anion exchange mechanism.

t
510 The kinetic studies referred that the adsorption reaction follows pseudo-second order model. The

ip
511 adsorption process is proceeds according to Langmuir isotherm, and the monolayer adsorption
512 capacity was found to the 0.606 mg/g at 25°C. This study indicated that EC/Cs composite could

cr
513 be used as an effective and promising low cost adsorbent for anionic dye removal from its

us
514 effluent.

515

516

an
M
d
p te
ce
Ac

22 Page 22 of 26
516 5. REFERENCES
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519 Ultrason Sonochem, 17(2), 383-390.

520 Al-Degs, Y. S., El-Barghouthi, M. I., El-Sheikh, A. H., & Walker, G. M. (2008). Effect of solution

t
521 ph, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon.

ip
522 Dyes and Pigments, 77(1), 16-23.

cr
523 Balcioglu, I. A., Arslan, I., & Sacan, M. T. (2001). Homogenous and heterogenous advanced
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us
525 Caparkaya, D., & Cavas, L. (2008). Biosorption of methylene blue by a brown alga cystoseira
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528
an
Dada, A. O., Olalekan, A. P., Olatunya, A. M., & DADA, O. (2012). Langmuir, freundlich, temkin
and dubinin-radushkevich isotherms studies of equilibrium sorption of zn2+ unto phosphoric acid
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529 modified rice husk. Journal of Applied Chemistry, 3(1), 38-45.

530 Dhanapal, V., & Subramanian, K. (2014). Recycling of reactive dye using semi-interpenetrating
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531 polymer network from sodium alginate and isopropyl acrylamide. Journal of Applied Polymer
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532 Science, 131(21).

533 DOULATI ARDEJANI, F., BADII, K., YOUSEFI LIMAEE, N., SHAFAEI, S. Z., & MIRHABIBI,
p

534 A. R. (2008). Adsorption of direct red 80 dye from aqueous solution onto almond shells: Effect of
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535 ph, initial concentration and shell type. Journal of Hazurdous Materials, 151(2-3), 730 - 737.

536 El-Zawahry, M. M. (1998). Decolorization of anionic dye solutions using water hyacinth
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537 derivatives. Bulletin of the National Research Centre (Cairo), 23(1), 11-22.

538 El-Zawahry, M. M., Hakeim, O. A., Abdelghaffar, F., & El-Hawary, N. S. (2014). Modification of
539 rice straw via polyelectrolyte layer-by-layer assembly for high performance dye adsorption.
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541 El-Zawahry, M. M., & Kamel, M. M. (2004). Removal of azo and anthraquinone dyes from
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543 Hameed, B. H., Mahmoud, D. K., & Ahmad, A. L. (2008). Equilibrium modeling and kinetic
544 studies on the adsorption of basic dye by a low-cost adsorbent: Coconut (cocos nucifera) bunch
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546 Hassabo, A. G. (2011). Synthesis and deposition of functional nano-materials on natural fibres (Vol.
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548 Hassabo, A. G., Mendrek, A., Popescu, C., Keul, H., & Möller, M. (2014). Deposition of

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549 functionalized polyethylenimine-dye onto cotton and wool fibres. Research Journal of Textile and

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550 Apparel, 18(1), 36-49.

551 Hassabo, A. G., Salama, M., Mohamed, A. L., & Popescu, C. (2015). Ultrafine wool and cotton

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552 powder and their characteristics. Journal of Natural Fibers, 12(2), 141-153.

553 Ho, Y. S., Wase, D. A. J., & Forster, C. F. (1996). Kinetic studies of competitive heavy metal

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554 adsorption by sphagnum moss peat. Environmental Technology, 17(1), 71-77.

555 Horvat, A. J. M., Babić, S., Pavlović, D. M., Ašperger, D., Pelko, S., Kaštelan-Macan, M., Petrović,
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556 M., & Mance, A. D. (2012). Analysis, occurrence and fate of anthelmintics and their transformation
557 products in the environment. TrAC Trends in Analytical Chemistry, 31(0), 61-84.
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558 Janaki, V., Oh, B.-T., Vijayaraghavan, K., Kim, J.-W., Kim, S. A., Ramasamy, A. K., & Kamala-
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559 Kannan, S. (2012). Application of bacterial extracellular polysaccharides/polyaniline composite for

560 the treatment of remazol effluent. Carbohydrate Polymers, 88(3), 1002-1008.
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561 Kadirvelu, K., Faur-Brasquet, C., & Cloirec, P. L. (2000). Removal of cu(ii), pb(ii), and ni(ii) by
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562 adsorption onto activated carbon cloths. Langmuir, 16(22), 8404-8409.

563 Kannan, N., & Sundaram, M. M. (2001). Kinetics and mechanism of removal of methylene blue by
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564 adsorption on various carbons--a comparative study. Dyes and Pigments, 51(1), 25-40.

565 Miretzky, P., & Muñoz, C. (2011). Enhanced metal removal from aqueous solution by fenton
566 activated macrophyte biomass. Desalination, 271(1–3), 20-28.

567 Mochochoko, T., Oluwafemi, O. S., Jumbam, D. N., & Songca, S. P. (2013). Green synthesis of
568 silver nanoparticles using cellulose extracted from an aquatic weed; water hyacinth. Carbohydrate
569 Polymers, 98(1), 290-294.

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570 Nasr, M. F., Abo El-Ola, S. M., Ramadan, A., & Hashem, A. (2006). A comparative study between
571 the adsorption behavior of activated carbon fiber and modified alginate i. Basic dyes adsorption.
572 Polymer - Plastics Technology and Engineering, 45(3), 335-340.

573 Nilsson, R., Nordlinder, R., Wass, U., Meding, B., & Belin, L. (1993). Asthma, rhinitis, and
574 dermatitis in workers exposed to reactive dyes. British Journal of Industrial Medicine, 50(1), 65-70.

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575 Sahmoune, M. N., & Louhab, K. (2010). Kinetic analysis of trivalent chromium biosorption by

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576 dead streptomyces rimosus biomass. The Arabian Journal for Science and Engineering, 35(2B), 69-

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577 80.

578 Sahmoune, M. N., Louhab, K., & Boukhiar, A. (2009). Biosorption of cr (iii) from aqueous

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579 solutions using bacterium biomass streptomyces rimosus. International Journal of Environmental
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581 Santos, R. M. d., Flauzino Neto, W. P., Silvério, H. A., Martins, D. F., Dantas, N. O., & Pasquini,
582 D. (2013). Cellulose nanocrystals from pineapple leaf, a new approach for the reuse of this agro-
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583 waste. Industrial Crops and Products, 50(0), 707-714.

584 Satapanajaru, T., Chompuchan, C., Suntornchot, P., & Pengthamkeerati, P. (2011). Enhancing
d
585 decolorization of reactive black 5 and reactive red 198 during nano zerovalent iron treatment.
586 Desalination, 266(1–3), 218-230.
te

587 Sivaraj, R., Namasivayam, C., & Kadirvelu, K. (2001). Orange peel as an adsorbent in the removal
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588 of acid violet 17 (acid dye) from aqueous solutions. Waste Management, 21(1), 105-110.
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589 Tran, C. D., Duri, S., Delneri, A., & Franko, M. (2013). Chitosan-cellulose composite materials:
590 Preparation, characterization and application for removal of microcystin. Journal of Hazardous
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591 Materials, 252–253(0), 355-366.

592 Vijayaraghavan, K., Won, S. W., & Yun, Y.-S. (2009). Treatment of complex remazol dye effluent
593 using sawdust- and coal-based activated carbons. Journal of Hazardous Materials, 167(1–3), 790-
594 796.

595 Wang, S., Boyjoo, Y., Choueib, A., & Zhu, Z. H. (2005). Removal of dyes from aqueous solution
596 using fly ash and red mud. Water Research, 39(1), 129-138.

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597 Wanyonyi, W., Onyari, J., & Shiundu, P. (2013). Adsorption of methylene blue dye from aqueous
598 solutions using eichhornia crassipes. Bulletin of Environmental Contamination and Toxicology,
599 91(3), 362-366.

600 Wasewar, K. L., Atif, M., Prasad, B., & Mishra, I. M. (2008). Adsorption of zinc using tea factory
601 waste: Kinetics, equilibrium and thermodynamics. CLEAN – Soil, Air, Water, 36(3), 320-329.

t
602 Xu, X., Gao, B.-Y., Yue, Q.-Y., & Zhong, Q.-Q. (2010). Preparation and utilization of wheat straw

ip
603 bearing amine groups for the sorption of acid and reactive dyes from aqueous solutions. Journal of

cr
604 Hazardous Materials, 182(1–3), 1-9.

605

us
606 Table 1 The values of the kinetic parameters as obtained from the experimental data
607 Table 2 Comparison between the parameters of adsorption isotherm models
608

an
609 Fig. 1 Chemical structure of C.I. Reactive Black 5 (RB5)
610 Fig. 2 Schematic illustration of the preparation of EC/Cs composite
611 Fig. 3 FT-IR spectrum of crude EC, purified EC, Cs and EC/Cs composite
M
612 Fig. 4 SEM micrographs of (a) crude EC, (b) Purified EC and (c) EC/Cs composite
613 Fig. 5 Contact angle measurements of (a) crude EC, (b) purified EC, (c) EC grafted with Cs
614 and (d) EC/Cs composite
615 Fig. 6 Effect of pH (a) and concentration-time curve (B) for the adsorption of RB5 onto the
d

616 surface of 10 g/l EC/Cs composite at 25°C, initial dye concentration of 40 mg/l
617 Fig. 7 Adsorbed dye concentration and efficiency of RB5 dye adsorption using 10 g/l EC/Cs
te

618 composite for different initial dye concentrations at 25°C, pH 3 and contact time 60 min.
619
620
p
ce
Ac

26 Page 26 of 26