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Digest Journal of Nanomaterials and Biostructures

Vol. 9, No. 1, January - March 2014, p. 45 - 52

West University of Timisoara, Faculty of Chemistry, Biology, Geography,
Department of Biology - Chemistry, 16 Pestalozzi, 300115 Timisoara, Romania.
West University of Timisoara, Multidisciplinary Research Platform “Nicholas
Georgescu - Roengen”, Advanced Environmental Research Laboratory,4 Oituz,
300086, Timisoara, Romania.
Low molecular weight chitosan, prepared as chitosan beads was used for the adsoption of
Tartrazine (TAR), Congo Red (CR) and Methyl Orange (MO). The efficiency of dyes
removal from aqueous solution was investigated, therefore samples containing various
concentrations of TAR, CR, and MO were mixed with chitosan beads and the adsorption
was estimated using a validated chromatographic method. The results provided by the
UPLC method were fitted to Freundlich, Temkin and Dubinin-Radushkevich adsorption
(Received September 30, 2013; Accepted December 19, 2013)
Keywords: Chitosan beads, Dyes removal, Dyes adsorption, Tartrazine, Congo Red,
Methyl Orange.

1. Introduction
Around 50% of all dye diversity is represented by azo dyes and due to their extensive
applications and persistence they pose a clear environmental hazard [1]. Tartrazine (TAR), Congo
Red (CR), and Methyl Orange (MO) (Figure 1) are azo colorings used commercially in paper,
foods, textiles, drugs and other products. These colorants cause adverse effects on human health if
their concentrations exceed the limits set by existing laws and regulations [2].
Because of the high stability of these dyes, conventional physico-chemical and biological
removal methods may not be completely effective for their elimination [3]. Adsorption is a popular
technique because of its simplicity and high efficiency, as well as the availability of a wide range
of adsorbents. It has proven itself an effective method for removal of various dyes from
wastewaters [4-8]. The adsorption process has an edge over the other treatment methods due to its
sludge free operation, and thorough removal of dyes even from dilute solutions [3].
There is a growing interest in finding low cost, locally available and effective materials for
the removal of dyes. Several non-conventional, low price adsorbents such as bentonite [9], leaf
[10], fly ash [11], activated red mud [12], rice husk [13], and fungi [14] have been used for the
removal of azo dyes from aqueous solutions. Unfortunately, not all of these adsorbents are
effective against anionic dyes due to their hydrophobic or anionic surfaces. Therefore, more
efficient adsorbents are needed [15].

Corresponding author:

MO. (c) congo red Biopolymers are promising biosorbents for the treatment of wastewater against dye pollution. bioadhesivity. the deacetylated form of chitin. and krill shells [17]. accurate. is a polymer composed of glucosamine residues linked by β-(1. Chitosan. chitosan. biodegradability. biocompatibility. 1 The chemical structures of industrial dyes: (a) tartrazine.46 NaO3S COONa N N HO N N (CH3)2N N N SO3Na SO3Na a b NH 2 SO3Na N N NaO3S N N H2N c Fig. as a means of their removal from wastewaters. 31]. sodium chloride. with 75-85% degree of deacetylation. Chitosan can be readily obtained from the alkali treatment of chitin and has many applications in various industries. the objective of this work was to develop a simple. Experimental 2. acetic acid and sodium hydroxide were purchased from Sigma Aldrich Chemie GmbH (Germany). 2. Among biopolymers. metal ions [20-22] and proteins [23] from aquatic environments. Recently. . In the present study. Due to the fact that there were signaled some examples of small fur and textile plants that have dumped wastewater containing CR. reproducible.4) glycosidic bonds. extracted mainly from crab. presence of a large number of hydroxyl and amino groups with high activity as adsorption sites. should be highlighted [16]. sensitive. abundance in nature. The extensive use of chitosan as a dye adsorbent is due to its high hydrophilicity. Many techniques have been employed for the assessment of azo dyes. a chitin derivative. UV-Vis spectroscopy coupled with a calibration method [26]. 29]. film-forming ability and most of all. CR. biomedicine. TAR. Reagents and Chemicals Chitosan with low molecular weight (LMW). because of its exceptional chelating behavior [24]. such as agriculture.1. environment. non-toxicity. HPLC-MS [30. UPLC [32]. the analysis technique used for the determination of azo dyes was based on a previously developed and validated UPLC method. such as UV-Vis spectroscopy [25]. giving special consideration to the discrimination between the three dyes in mixtures [33]. shrimp. HPLC [25. several studies brought attention to the high potential of chitosan for the adsorption of dyes [19]. prawn. and rapid method for the adsorption of mixtures of the three dyes onto chitosan beads. Chitin is itself a waste product of the seafood processing industry. cosmetics and food [18]. MO and TAR into rivers. economical. ELISA [27] potentiometry [28]. (b) methyl orange. All other chemical were analytical-reagent grade.

For the sake of simplicity and for time-efficiency.75 µg L-1 and 30 µg L-1 were obtained by diluting with ultrapure water the appropriate volume of TAR. by placing approx.001 mg mL-1). via Hemtek. areas of the peaks were used in all equations.3. and MO were prepared in 0.1 M acetate buffer in 10% MeOH as mobile phase B: equilibration with 50% mobile phase A. with a constant speed of 300 rpm at 25±1ºC. The elution was performed at 0. Ae is the final (equilibrium. Samples from the adsorption experiments mixtures were taken at zero and 2 hours time and injected in the chromatographic system. the chitosan gel was turned into spherical homogeneous chitosan gel beads.1 M sodium chloride solution (TAR 1. Romania) consisted in Acquity Binary Solvent Manager. and re-equilibration [33]. Bucharest. which neutralized the acetic acid within the chitosan solution and. at 2 hours in our case) area of the peak representing the same dye (mg L-1). qe (mg g -1).0048 mg mL-1. The adsorption of a mixture of these dyes was carried out in a batch process at room temperature (25±1°C). CR 1.4 g) employed. Serbia and Chromaktiv. Temkin and Dubinin-Radushkevich isotherm models) were applied.3 mL min-1. Prior to the measurements the chitosan beads were kept at 4ºC. MO. after adding a few drops of chloroform in order to avoid bacterial degradation. 0. Preparation of Chitosan Beads The chitosan solution was prepared by dissolving approximately 1. various dye concentrations were tested.3 min. MO. and MO stock solutions. The UPLC method was tested for applicability in determining the concentration of TAR.5 min to 70% mobile phase A. V is the volume of dye solution (20 mL) and W is the weight of chitosan beads (0. then increase to 100% mobile phase A in 0.2. using the following gradient elution program made with 100% MeOH as mobile phase A and 0. Acquity Sample Manager and Acquity PDA Detector (set to collect data between 210 and 500 nm) and an Acquity UPLC BEH C18 2. and CR from water phase onto chitosan beads.1 mm x 50 mm column (1. 2. The wet chitosan gel beads were extensively rinsed with distilled water to remove any NaOH and sieved on 1 mm mesh. and CR from aqueous solutions that were submitted beforehand to adsorption onto chitosan beads. Adsorption Experiments For adsorption isotherm studies.5 min. was determined with the relation: q ‐ (1) where A0 is the initial area of the peak representing a dye (µV s) at the beginning of the adsorptions experiment. CR. Belgrad.47 Standard stock solutions of TAR. The viscous solution was left overnight before adding drop wise into a precipitation bath containing 500 mL of 0. instead of concentrations. Diluted standard solutions were obtained in and the adsorption experiments were carried out in acetate buffer (pH 5. The Freundlich isotherm [34] is an empirical equation that comprises the heterogeneity of sites and the presence of multilayer of adsorption sites with growing energies Equation 2. In order to describe the removal mechanism of TAR. For these analyses it was used an UPLC system (Milford. was used for the adsorption process.008 mg mL-1. The adsorption capacity of adsorbent material.7 µm particle diameter).00 g chitosan powder into 30 mL of 2% acetic acid solution.5 min.6. CR. three widely used isotherm models (Freundlich. hold the equilibration conditions 0. USA. Solutions of dyes with concentrations between 0. linear increase till 1. thus. A themostated shaker (Vibramax 100 Heidolph). 2. q KA / (2) . and respectively MO 1. continuous stirring. 0.4 g of chitosan beads in 20 mL of dye solutions and were stirred at 300 rpm for 2 hours. The aqueous NaOH solution was kept under a mild.5 M NaOH. hold this condition for 0. The batch adsorption experiments were conducted in 50 mL Erlenmeyer glass flasks.1 M).

1. as Equation 6: (6) where qe is the adsorption capacity (mg g-1). The Dubinin–Radushkevich isotherm model [38] is a temperature-dependent twoparameter isotherm that describes the porous structure of the sorbent. Ae is the area of the peak describing a dye in aqueous phase at equilibrium. R is the universal gas constant (8. representing the maximum binding energy. based on the linear form of the Dubinin-Radushkevich equation (Equation 8). and afterwards. and constant B is related to the heat of adsorption and its value is . The Temkin isotherm. Results and Discussion 3. the more heterogeneous the solid phase surface is [35]. as a consequence of interactions between an adsorbent and the adsorbate [36]. ∆ conclusions can be drawn regarding whether the adsorption process is an exothermic or endothermic reaction. the value of the bF factor should be between 0 and 1. kDR (mol2 K J-2) are DubininRadushkevich isotherm constants and ε is given by the relation: ε RT 1 (7) where Ae is the area of the peak describing a dye in aqueous phase at equilibrium. respectively. as can be observed from the linear form of Freundlich equation (Equation 3): lnq lnK lnA (3) Furthermore. a plot was done of lnqe as function of ε2. (8) 3. If the adsorption process is described by chemisorptions. is given bellow: q q BlnK A BlnK (4) BlnA (5) where K0 (L g-1) is the equilibrium binding constant. both the peak areas and . From the value of B. qDR (mg g-1). A plot of qe versus lnAe facilitates the determination of the isotherm constants B and K0 from the slope and intercept of the straight line plot [37]. The Temkin isotherm equation predicts that the heat of adsorption of all the molecules in the layer reduces linearly with the filling of empty adsorption sites. in its non-linear Equation 4 and linear Equation 5 forms. which represents the slope of the straight line obtained from the previously mentioned plot.314 J mol-1 K-1) and T is the temperature (ºK) at which the adsorption process took place.48 where qe is the amount of dye adsorbed at equilibrium per mass of chitosan (mg g-1). The value of bF describes the adsorption intensity or the surface heterogeneity. the resulting peak area values were used to determine the value of the adsorption capacity. The linear Dubinin-Radushkevich equation is given below. The closer the value of bF is to 0. the Freundlich coefficients n and Kf are obtained from plotting lnqe as a function of lnAe. from the linear form of Freundlich equation the factor bF can be determined. The Dubinin-Radushkevich mechanism of adsorption is defined by a Gaussian energy distribution onto the heterogeneous surface of the sorbent [39]. Adsorption experiments Following the adsorption of dyes onto chitosan beads. In order to obtain the values of the isotherm constants. Its value can be calculated as 1/n.

0 11. 3.0 11. linearized according to Freundlich equation.0 10. Freundlich.0 ln Ae Fig.0 10. Adsorption isotherms of TAR. i.5 12. for all three dyes.5 10.5 11.5 10. Freundlich and Dubinin-Radushkevich isotherms.5 11.5 13. Figures 2. Temkin and Dubinin-Radushkevich.5 12.49 adsorption capacity values were fitted to three theoretical isotherm models. 3 and 4 present.0 12. linearized according to Temkin equation.0 12. the linear representation of the Temkin.0 lnAe Fig.5 13.e. Tartrazine Congo Red Methyl Orange 250000 q e (absorption capacity) 200000 150000 100000 50000 0 9.0 9. CR and MO on the chitosan beads. 2 Adsorption isotherms of TAR.0 9. . CR and MO on the chitosan beads. Tartrazine Congo Red Methyl Orange 13 12 lnqe 11 10 9 8 7 9.

000121 0.0999 1.0 -6 1. 4.9638 3.0566 0.9912 0.0x10 -6 5. linearized according to Dubinin-Radushkevich equation.9908 0. Freundlich isotherm model also provides some hints regarding aspects of the mechanism of adsorption.5041 6.3333×104 0. ΔQ was calculated and for all three dyes its value was higher than 0.0089 0. R2>0.988).9916 484. consequent with data from literature [41].9244 0.8774×103 2.0x10  -6 4. Experimental isotherm constants and correlation coefficients for the adsorption of TAR.6081 0. Also from the linear Temkin equation.50 Tartrazine Congo Red Methyl Orange 12 11 lnqe 10 9 8 7 0. Adsorption isotherms of TAR.1258×104 0. and MO onto chitosan beads using experimental data Constant Freundlich model n KF ((mg g-1)(mL mg-1)) bF R2 Temkin model K0 (L mg-1) R2 Dubinin-Radushkevich model kDR (mol2 K J-2) qDR (mg g-1) R2 TAR CR MO 1. The primary observation is that the Temkin equation is the best model to describe dyes adsorption on the chitosan beads under the concentration range studied (correlation coefficient.2997×105 0. it can be suggested that the adsorption of the two dyes onto chitosan beads is described by chemisorptions.0x10 2 Fig. corresponding to data regarding azo dyes from literature [40]. Due to the fact that the bF constant has values lower than 1 for TAR and MO.49594×10-5 0.9464 0.0x10 -6 3.988 1.1047 1. CR. .9745 3. CR and MO on the chitosan beads. proving that the adsorption of dyes onto chitosan beads is an exothermic reaction.9729 Table 1 lists the calculated results (adsorption constants and correlation coefficients) for the adsorption processes.7535 0.0818 0.0x10 -6 2.9722 0. Table 1.2298×10-5 0.0x10 -6 6.9582 40.8891 1.

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