Desalination 263 (2010) 233239

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Adsorption equilibrium and kinetics of U(VI) on beta type of akaganeite

Sabriye Yusan , Sema Akyil Erenturk
Ege University Institute of Nuclear Sciences 35100 Bornova-Izmir, Turkey

a r t i c l e

i n f o

a b s t r a c t
The use of cheap, high efciency and low-risk adsorbent has been studied for the removal of U(VI) from aqueous solutions. A series of experiments was conducted in a batch system to assess the effect of the system variables, i.e. initial pH, temperature, initial uranium concentration and contact time. The results of these parameters were given in the previous work. In this paper Langmuir, Freundlich, Temkin, Dubinin Radushkevich (DR) and HarkinsJura isotherms were used to analyze the equilibrium data at different temperatures. Adsorption process tted to Langmuir and Temkin isotherm models. Also the adsorption kinetics was found to follow pseudo-second-order rate kinetic model, with a good correlation (R2 N 0.99) and intraparticle diffusion as one of the rate determining steps. The ndings of this investigation suggest that the chemical sorption plays a role in controlling the sorption rate. 2010 Elsevier B.V. All rights reserved.

Article history: Received 15 March 2010 Received in revised form 24 June 2010 Accepted 25 June 2010 Available online 24 July 2010 Keywords: -FeOOH U(VI) Adsorption Isotherms Kinetic

1. Introduction Iron oxides, as a group, have important applications as pigments, catalysts, gas sensors, magnetic recording media, etc. [1]. Among these iron oxides, akaganeite has attracted much investigation because of its unique sorption, ion exchange, and catalytic properties [2]. For instance, akaganeite used as a low-cost potential adsorbent for the removal of hexavalent chromium, U(VI), As(V) and As(III) from aqueous solutions was studied by some authors [36]. Furthermore, akaganeite is used as a precursor in the production of other iron oxide phases such as hematite, goethite and magnetite in order to obtain particle morphologies that are unusual in these iron oxide phases. In this way, akaganeite is indirectly useful in industrial and biomedical applications associated to other iron oxide phases [7]. Akaganeite from the Akagane mine in Japan was rst described as the naturally occurring form of -FeO(OH) [8]. It has since been recognized as a major Fe-oxide component in soils and geothermal brines. Akaganeite, -FeO(OH), is often observed as a corrosion product of some steels in chloride-containing environments, i.e. marine atmospheres. It occurs commonly in corroded archeological iron artifacts and is known to form continuously even in the controlled atmosphere of museums [9]. The crystal structure is well determined since the work of Mackay [10,11] who showed that it is of the hollandite type [12]. It is often assumed that the tunnels which are parallel to the c axis of the tetragonal structure can be occupied by chloride ions and water molecules.

Corresponding author. Tel./fax: +90 232 3886466. E-mail address: sabriye.doyurum@ege.edu.tr (S. Yusan). 0011-9164/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.2010.06.064

Uranium is a natural element and can be found in soils and rocks. In contact with water, it can be mobilised and, therefore, is found in many groundwaters as a trace component. Naturally occurring uranium has very low levels of radioactivity. Its danger for human health mostly results from its properties as a heavy metal [13]. There is increasing interest in searching for different adsorbents, such as activated carbon [14,15], metal oxides, aluminosilicates [1618], goethite [19] for the uranium elimination from the aqueous environment. Uranium occurs as a mobile, aqueous uranyl UO2+ ion 2 in nuclear wastes as well as in mill tailings, wastes material of uranium mining, where soil and mine-water contamination plumes have very high dissolved solutions and solid uranium concentrations [20]. In the present study, akaganeite (-FeOOH) which is synthesized and as mentioned previous work was used as a sorbent. In the previous work (-FeOOH) was synthesized in the laboratory by precipitation from aqueous solutions of Fe(III) chloride and two different precipitating agent and adsorbents obtained were called as Akaganeite-1 (AK-1) and Akaganeite-2 (AK-2). In that paper, the relative importance of test parameters like solution pH, contact time, temperature and concentration of adsorbate on adsorption performance of akaganeite for U(VI) ion were studied. And according to results, AK-1 has a higher adsorption capacity than AK-2. The maximum U(VI) removal in AK-1 was obtained as N 99% at pH 4.0 0.1 at initial concentration of 50 mg L 1 and amount of akaganeite equal to 0.01 g. The experimental results have been analyzed by Langmuir, Freundlich and DubininRadushkevich (DR) adsorption isotherms and results showed that adsorption equilibrium data of AK1 and AK-2 tted to Freundlich and Langmuir. The results of the thermodynamics of U(VI) ion/akaganeite system indicate spontaneous and endothermic nature of the process. Also AK-1 and AK-2 were

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characterized by powder X-ray diffraction for crystalline phase identication and scanning electron microscope (SEM). In the current, the applications of the isotherm models have been studied to explain the adsorption characteristics of the akaganeite. For this aim, Langmuir, Freundlich, Temkin, DubininRadushkevich (DR) and HarkinsJura isotherms were used to analyze the equilibrium data at different temperatures. And furthermore, kinetics as well as the diffusion parameters for the adsorption of U(VI) onto the akaganeite is evaluated which are not studied in the previous work XRD, BET and FT-IR analysis are also discussed for characterization studies given in the previous paper. 2. Materials and methods 2.1. Materials Synthesis of akaganeites (AK-1 and AK-2) was rst reported in our previous study [4]. All chemicals and reagents used for experiments and analyses were of analytical grades. A stock solution of 1000 mg L 1 U(VI) was prepared by dissolving an appropriate amount of UO2(NO3)26H2O in deionized water. The initial pH of the working solutions was adjusted by addition of HNO3 or NaHCO3. Dibenzoyl methane-tri-n-octyl phosphine oxide (DBM-TOPO), salicylic acid was obtained from Merck Co. The buffer solutions (pH 4, 7 and 9) to calibrate the pH-meter Model 8521 from Hanna Instruments were also purchased from Merck. 2.2. Batch adsorption experiments Batch adsorption experiments were carried in a thermostated shaker bath, GFL-1083 model. AK-1 and AK-2 (0.01 g), which have 75 m particle sizes, were added to 10 ml solution containing various uranium concentrations at different temperatures for various contact time. The pH was adjusted by adding HNO3 and Na2CO3 to the solutions at the each experiment. The suspension was ltered by using Whatman lter paper No: 44. A simple and sensitive spectrophotometric method was used in the experiments to determine uranium in solution. The uranium remained in solution was analyzed with the DBM-TOPO as complexing agent at 405 nm against reagent blank employing spectrophotometric method on Shimadzu UV-1601 UVVIS spectrophotometer [21,22]. The amount of adsorbed uranium was estimated from the difference of the uranium concentrations in the aqueous phase before and after the adsorption. Each experiment was repeated at least three times and the results given are the average values. The percentage adsorption of uranium from aqueous solution was computed as follows: Adsorption % = Cint Cfin =Cint 100 1

were collected at room temperature in the range of 2 between 0 and 70. The diffractograms of AK-1 and AK-2 are shown in Fig. 1(a) and (b). All diffraction patterns contain only the diffraction lines characteristic of -FeOOH (JCPDS card 34-1266). The corresponding Miller indices are marked above the diffraction lines [23]. All XRD patterns exhibit the characteristic anatase diffraction peaks at 2 values of AK-1 and AK-2: 35.3, 26.9, 11.9, 56.2 and 16.9; 35.2, 26.8, 11.9, 56.1 and 16.8, respectively. This adsorbent has low crystallinity with d values. Similar result has been obtained in the literature [2326]. DebyeScherrer diffraction patterns are often used to characterize samples, as well as to probe the structure of nanoparticles [27]. We also estimated the particle sizes of the synthesized AK-1 and AK-2 from the line width as 8.64 and 17.35 nm, respectively using the DebyeScherrer equation: L = k = B cos 2

where L is the length of the crystal in the direction of the d spacing, k is a shape factor of the particle (1 if spherical, typically 0.9 is used), B is the line width at half maximum, and are the wavelength and incident angle of the X-rays, respectively [28]. Nitrogen multipoint BET analysis yielded a specic surface of AK-1 and AK-2, 109.06 and 75.40 m2 g 1, respectively. The average pore radius (nm) was found for AK-1 and AK-2 as 3.97 and 8.53. Incremental pore volume (cm3 g 1) was 0.14 and 0.24, respectively. Khasanova et al. and Barrero et al. measured the BET surface area of 41.7 and 25 m2 g 1, respectively [29,30]. Cornell and Schwertmann, Solozhenkin et al., Parida et al., Watkins et al. and Martnez-Llad et al. obtained similar surface area of our work [5,3134]. FT-IR spectroscopy was performed on an IRPRESTIGE-21 Shimadzu FT-IR spectrometer. The sample was prepared with KBr and pressed

where Cint and Cn are the initial and nal uranium concentration, respectively. Kinetics of adsorption was determined by analyzing adsorptive uptake of the U(VI) from aqueous solution at different time intervals. For adsorption isotherms, U(VI) solutions of different concentrations (50200 mg L 1) and at different temperatures (2050 C) were agitated with known amounts of adsorbents until the equilibrium was achieved. 2.3. Material characterization methodology and intermediate results Scanning electron microscope (SEM) images were taken on Jeol Jsm 6060 scanning electron microscope. The SEM images showed that crystallites in both products had similar cigar-like shapes and similar crystal sizes [4]. Powder X-ray diffraction (XRD) data were collected on a SHIMADZU XDD-6000 diffractometer with Cu-X radiation ( = 1.5405 ). The data

Fig. 1. X-ray diffractogram of the akaganeite (a) AK-1. (b) AK-2.

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into pellet. As shown in Fig. 2, the spectrum of Akaganeite was collected in the mid-IR range from 400 to 4000 cm 1 with a resolution of 1 cm 1. Infrared spectra were used, for instance, to study the strength of the hydrogen bonds of iron(III) oxide hydroxides [35]. The infrared spectra of akaganeite (AK-1 and AK-2) were obtained with the KBr presseddisk technique and are presented in Figs. 3 and 4. The spectral regions of interest are the HOH banding region (~ 1630 cm 1) and the OH stretching region of H2O (~3400 cm 1). Sorbed water contributes to the HOH banding region (~ 1630 cm 1) and the OH stretching region of H2O (~ 3400 cm 1). In akaganeite OH.Cl bonds are formed instead of OHO bonds, with HCl ions being much weaker hydrogen bond acceptors than OH and O 2 ions. So there are two sets of librations due to hydrogen bonds, those of OH librational ROH 847 and 820 cm 1 and those of 697 and 644 cm 1, due to the two OH.Cl hydrogen bonds present. In the nanocrystalline sample prepared in the laboratory, the bands at 847 and 820 cm 1 were diminished and mostly disappeared due to the washing of the chlorine ions. The cooperativity of hydrogen bonds such as OHOHOH may result in the band at 1064.5 cm 1. The energy translational mode of akaganeite due to the FeO stretches was observed at ~ 482 cm 1 [31,36].

Fig. 3. Lagmuir isotherm plots for the sorption of U(VI) on AK-1.

3. Results and discussion 3.1. Results of adsorbent characterization The XRD analysis conrmed that iron(III) oxyhydroxides prepared in this study were crystalline and from the BET results they have high surface area and it improves the sorption capacity.

Fig. 2. FT-IR spectrum of Akaganeite nanoparticle, (a) AK-1. (b) AK-2.

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for some temperatures especially for AK-2 adsorbent due to data scatter. The values of Qm and KL was showed variation with increase in temperature. Adsorption capacity and intensity of adsorption are more stable at lower temperatures for the removal of U(VI) ions from aqueous efuent. Further, it conrmed the fact that an endothermic process and exothermic process took place in this adsorption system for AK-1 and AK-2, respectively [37]. Also difference of the process may be due to major complexes which are seen in the range of acidic to near neutral pH values. 3.2.2. Temkin isotherm equation This isotherm was rst developed by Temkin and Pyzhev [38], and it is based on the assumption that the heat of adsorption would decrease linearly with the increase of coverage of adsorbent [39]. They considered the effects of some indirect adsorbate/adsorbate interactions on adsorption isotherms. They suggested that, because of these interactions and ignoring very low and very large values of concentration, the heat of adsorption of all molecules in the layer would decrease linearly with coverage [40]: qe = RT = bt lnKt Ce : Eq. (4) can be linearized as qe = B1 ln Kt + B1 ln Ce 5 4

Fig. 4. Lagmuir isotherm plots for the sorption of U(VI) on AK-2.

From the FT-IR spectra it is speculated that uranium ions reacted rather directly with Fe substituted surface OH2 functional groups of akaganeite. And the surface complexes, SOUO2+ and SOUO2OH, can be used to interpret the sorption of U(VI) on akaganeite. This suggests that there is a specic adsorption between the uranium anions and the adsorbent, thus the substitution of SOH groups by U(VI) ions plays an important role in the adsorption mechanism. The fact that uranium ions are possibly coordinated to discrete surface iron cations is supported by FT-IR results. 3.2. Adsorption equilibrium study Equilibrium data, commonly known as adsorption isotherms, are basic requirements for the design of adsorption systems. The sorption data have been subjected to different sorption isotherms, namely Langmuir, Freundlich, Temkin, DR, HarkinsJura, Halsey sorption and Handerson isotherms. For each isotherm, the temperature of solution was varied to 2050 C. According to results, AK-1 and AK-2 sorption data tted Langmuir and Tempkin isotherm models. 3.2.1. Langmuir isotherm equation The basic assumption of Langmuir adsorption isotherm is based on monolayer coverage of the adsorbate on the surface of adsorbent. The saturated monolayer can be represented by the following equation: Ce = qe = 1 = Qm KL + Ce = Qm 3

where B1 = RT/b, in which R is the gas constant, T the absolute temperature in Kelvin, bt the constant related to the heat of adsorption and Kt is the equilibrium binding constant (mg L 1). The Temkin isotherm equation has been applied to describe adsorption on heterogeneous surface [41,42]. The constants obtained for Temkin isotherm are shown in Table 1. The Temkin constant, B1, shows that the heat of adsorption increases with the increase in temperature for AK-1, however, the heat of adsorption decreases with the increase in temperature, indicating endothermic and exothermic adsorption for AK-1 and AK-2, respectively (Figs. 5 and 6). 3.3. Adsorption kinetics To evaluate sorption as a unit operation, it requires consideration of two important physico-chemical aspects of the process: the kinetics and the equilibria of sorption. Kinetics of sorption describing the solute uptake rate, which in turn governs the contact time, is one of the important characteristics dening efciency of sorption. The study of the equilibrium established in any liquidsolid system is important in determining distribution of the solute between the solid and liquid phases and determining feasibility and capacity of the sorbent for sorption [43]. In order to determine kinetic parameters and explain to the mechanism of the adsorption processes, lots of researchers have used rst and pseudo-second-order rate expressions [44]. Three kinetic models were applied to adsorption kinetic data in order to investigate

where Ce is the equilibrium concentration of the adsorbate, qe is the amount of the adsorbate adsorbed at equilibrium, Qm and KL are Langmuir's constants related to the capacity and energy of the adsorption, respectively. The linear nature of the curve was found by plotting Ce/qe versus Ce at different temperatures (Figs. 3 and 4) suggested the applicability of Langmuir isotherm for the present system. The values of Qm and KL at different temperatures were determined from the slopes and intercepts of the respective plot and presented in Table 1. As you see from Table 1, R2 values are very low
Table 1 Values of Langmuir and Temkin isotherm constants. Isotherm parameters Temperature (K) AK-1 Langmuir KL (g L 1) Qm (mmol g 1) R2 Temkin B1 KT (g L 1) R2 293 80 2500 0.976 3406 0.22 0.971 303 16.67 1000 0.995 2564 1.39 0.969 313 1.825 137 0.607 3329 2.7 11 0.889

AK-2 323 50 2000 0.973 12,027 2.86 0.633 293 100 2500 0.765 50,300 0.17 0.944 303 10 500 0.725 38,808 0.04 0.860 313 1.5 333 0.838 20,724 1.22 0.283 323 16.67 10,000 0.922 23,690 0.23 0.137

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Fig. 5. Tempkin isotherm plots for the sorption of U(VI) on AK-2.

the behavior of adsorption process of U(VI) onto Akaganeite. These models are the pseudo-rst-order [45], the pseudo-second-order [28] and the intraparticle diffusion models [46]. The adsorption of U(VI) from a liquid phase to solid phase can be considered as a reversible process with equilibrium being established between the solution and solid phase. Adsorption phenomenon can be described as the diffusion control process, assuming a non-dissociation molecular adsorption of U(VI) on akaganeite nanoparticles [46]. The Lagergren rst-order rate expression based on solid capacity is generally expressed as follows: logqe qt = log qe k1 t 2:303 6

Fig. 7. Lagergren rst-order plot for the adsorption of U(VI) by AK-1 and AK-2.

where qt and qe (mg g 1) are the amounts of the metal ions sorbed at equilibrium (mg g 1) and t (min), respectively, and k1 is the rate constant of the equation (min 1). The adsorption rate constants (k1) can be determined experimentally by plotting of ln(qe qt) versus t [45]. A plot of Eq. (6) is shown in Figs. 7 and 8 for AK-1 and AK-2. Table 2 shows the rate constants and R2 values of the kinetic models. The experimental data gives not good t for both AK-1 (R2 = 0.8075) and AK-2 (R2 = 0.2375) indicating that the Lagergren model is not applicable for these adsorbents. The pseudo-second kinetic model developed by Ho and McKay, is based on experimental information of solid phase sorption, generally it has been applied to heterogeneous systems, where the sorption mechanism is attributed to chemical sorption and the sorption capacity is proportional to the number of active sites on the sorbent. The model can be represented by the following equation [46]: t 1 t = + qt qmax k2 q2 max 7

The plot for the above equation is shown in Figs. 9 and 10. The data gives perfect t for this model for both AK-1 (R2 = 0.999) and AK-2 (R2 = 0.989). The values of the second-order rate constant found from the slopes of the plots for AK-1 (k2 = 0.17 g mg 1 min 1) and AK-2 (k2 = 0.10 g mg1 min 1) indicate that U(VI) removal rate is faster by AK-1 than AK-2. Based on the obtained correlation coefcients (r), the experimental data conformed better to the pseudo-second-order equation, evidencing chemical sorption as rate-limiting step of adsorption mechanism [47]. The pseudo-second-order model is based on the assumption that the rate-limiting step may be chemisorption involving valence forces through the sharing or exchange of electrons between adsorbent and adsorbate [48]. Another tested simplied kinetic model to the sorption process was the intraparticle transport [49]. The kinetics of sorption of U(VI) on the AK-1 and AK-2 was also evaluated by the MorrisWeber equation [50]: qt = kp t
0:5

where qt is the concentration of the sorbed ion (mg g 1) at time t, and kp is the rate constant for the intraparticle transport (mg g 1 h 0.5). According to this model, a graphic plot for qt versus t0.5 could predict the sorption mechanism. If a straight line (passing through the point of origin) is obtained, therefore, sorption of the ions onto the impregnated sorbent followed a diffusion mechanism [51]. When pore diffusion limits the adsorption process, the relationship between the initial solute concentration and the rate of adsorption will not be linear. Besides for the adsorption on the outer surface of adsorbent, there is also possibility of transport of

where k2 (g mol 1 min 1) is the second-order rate constant. The linear plot of t/qt as a function of t provided not only the rate constant k2, but also an independent evaluation of qe. The results are given in Table 2.

Fig. 6. Tempkin isotherm plots for the sorption of U(VI) on AK-1.

Fig. 8. Pseudo-second-order plot for the adsorption of U(VI) by AK-1 and AK-2.

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Table 2 Values Lagergren rst-order model, pseudo-second-order model and Weber and Moris model constants. Adsorbent AK-1 AK-2 k1 (dk 1) 0.005 0.02 0.004 0.04 R1 0.81 0.24 k2 (g/mg dk) 0.17 0.01 0.10 0.05 R2 0.999 0.989 kp (mg/g dk0.5) 1010 1.29 743 2.22

adsorbent ions from the solution to the pores of the adsorbent due to stirring on batch process. This possibility was tested in terms of intraparticle diffusion model. The linear portion of the plot for a wide range of contact time between the adsorbate and adsorbent does not pass through the origin. This deviation from the origin or near saturation may be perhaps due to difference in the rate of mass transfer in the initial and nal stages of adsorption. Further such deviation from the origin indicated that the pore diffusion is not the rate-limiting step [47]. From Fig. 9, it can also be observed that the straight lines does not pass through the origin, which indicates that intraparticle diffusion and lm diffusion are both the rate-limiting steps for U(VI) diffusion onto AK-1 and AK-2 [52]. The Reichenberg equation [53] was applied to check that sorption proceeds via lm diffusion or intraparticle diffusion mechanism. Reichenberg equation was tested in the following way [53]: X=   B t 6 e 1 2 9

Fig. 10. Reichenberg plot for the adsorption of U(VI) by AK-1 and AK-2.

sorbent for removing U(VI) from aqueous solution because of its high adsorption capacity, low-risk feature.

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where X = qt/qe and Bt is a mathematical function of X which can be calculated for each value of X as. Bt = 0:4977 ln1X 10

A plot of Bt versus t is also shown in Fig. 10, which is a straight line. It is clear from it that intraparticle diffusion is the rate controlling step with a small friction of the sorption that occurs through lm diffusion because the plot does not pass through origin [54]. 4. Conclusion The present study focuses on adsorption of U(VI) from aqueous solution using the Akaganeite as a low cost and effective nanocrystal sorbent. The adsorption equilibrium and kinetics have been examined. The experimental data were evaluated by Langmuir and Temkin isotherms. According to isotherm data, adsorption process is endothermic for AK-1 and exothermic for AK-2. Kinetic evaluation of the equilibrium data showed that the adsorption of U(VI) on Akaganeite followed well the pseudo-secondorder kinetic model and the lm diffusion and intraparticle diffusion are both the rate-limiting steps. Based on all the results, it can be also concluded that the -FeOOH, Akaganeite is an effective and alternative

Fig. 9. Weber and Moris plot for the adsorption of U(VI) by AK-1 and AK-2.

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