Journal of Environmental Radioactivity 100 (2009) 162166

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Journal of Environmental Radioactivity

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Removal of uranium (VI) from aqueous solution by adsorption of hematite

Xie Shuibo a, b, *, Zhang Chun a, Zhou Xinghuo a, Yang Jing a, Zhang Xiaojian b, Wang Jingsong a
a b

School of Urban Construction, University of South China, Hengyang, Hunan 421001, PR China Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084, PR China

a r t i c l e i n f o
Article history: Received 13 February 2008 Received in revised form 2 August 2008 Accepted 19 September 2008 Available online 19 December 2008 Keywords: Hematite Uranium (VI) or U (VI) Adsorption Adsorption isotherm

a b s t r a c t
Hematite, a type of inorganic-sorptive medium, was used for the removal of U (VI) from aqueous solutions. Variables of the batch experiments including solution pH, contact time, initial concentration, temperature, calcium and magnesium ions were studied. The results indicated that the adsorption capacities are strongly affected by the solution pH, contact time and initial concentration. A higher pH favors higher U (VI) removal. The adsorption was also affected by temperature and calcium and magnesium ions, but the effect is very weak. The maximum adsorption capacity (qm) only increased from 3.36 mg g1 to 3.54 mg g1 when the temperature was increased from 293 K to 318 K. A two-stage kinetic behavior was observed in the adsorption of uranium (VI): very rapid initial adsorption in a few minutes, followed by a long period of slower uptake. It was found that an increase in temperature resulted in a higher uranium (VI) loading per unit weight of the sorbent. The adsorption of uranium by hematite had good efciency, and the equilibrium time of adsorbing uranium (VI) was about 6 h. The isothermal data were tted with both Langmuir and Freundlich equations, but the data tted the former better than the latter. The pseudo-rst-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model were used to describe the kinetic data, but the pseudo-second-order kinetic model was the best. The thermodynamic parameter DG0 were calculated, the negative DG0 values of uranium (VI) at different temperatures conrmed the adsorption processes were spontaneous. 2008 Elsevier Ltd. All rights reserved.

1. Introduction Contamination of groundwater resources by working and outof-commission uranium mining operations is a well-known environmental problem. The threat posed to the environment arises not only from the radioactive emissions from uranium series radionuclides, but also from the chemical toxicity of uranium (Bargar et al., 1999, 2000). Based on the radiological risk by radiation of uranium isotopes and chemical risks from heavy metals, the health effects of uranium can be divided into carcinogenic and non-carcinogenic effects (WHO, 1998; Health Canada, 1999). The US EPA has classied uranium as a conrmed human carcinogen (group A), and has suggested that zero tolerance is the only safe acceptable limit for the carcinogenic risk from uranium. They prescribed the maximum contaminant level goal (MCLG) for uranium as zero in 1991. In addition, the EPA nalized the realistic regulation level of 30 mg l1 as the maximum contaminant level (MCL) (US EPA, 1999b). Canada proposed an interim maximum acceptable level (IMAC) of 20 mg l1,

* Corresponding author. School of Urban Construction, University of South China, 28 West Changsheng Road, Hengyang, Hunan 421001, PR China. Tel.: 86 734 8282741; fax: 86 734 8280805. E-mail address: xiesbmr@263.net (X. Shuibo). 0265-931X/$ see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.jenvrad.2008.09.008

and the WHO strictly recommended a reference level of 2 mg l1 (Shin et al., 2002). Since dissolved toxic metal ions can eventually reach the top of the food chain and thus are a latent risk factor for both humans and animals, great importance has been attached to the threat that the nuclear industry poses to the environment, especially from the leaching of U (VI) from uranium mine tailings to the groundwater. One large-scale uranium mine tailing in South China has been in operation for almost forty years and rudimental radioactive nuclides have led to the pollution of the surface water and groundwater to various extents (Ohnuki et al., 1997; Hsi and Langmiur, 1985; Waite et al., 1994; Ma and Wang, 2000; Shuibo et al., 2005). The tolerance limit for the discharge of U (VI) into waters is 50 mg l1. Uranium exists in aqueous solution under oxidation conditions as the linear dioxo UO2 cation. Therefore, various 2 processes such as chemical precipitation, ion exchange, membrane separation and activated carbon adsorption have been employed to remove metal pollutants from aqueous solutions. However, most of these methods suffer from some disadvantages including incomplete metal removal, toxic sludge generation and high cost when applied to dilute efuents on a large scale (Catherine et al., 2004). Recently, permeable reactive barriers (PRBs) have become established as an economical technology for treatment of contaminated groundwater in situ. PRB represents a tested

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environmental remedial technology for treatment of groundwater contaminated with a wide array of both organic and inorganic contaminants (Gillham et al., 1994; Blowes et al., 2000). PRB systems consist of a permeable treatment zone that is inserted underground in a natural aquifer and intercepts the pollution plume carried within the aquifer. The barrier can be a simple trench lled with reactive material. For PRB treatment to succeed, it is essential that there be no disruption of the natural groundwater ow; otherwise the water may bypass the reactive zones. One challenge to overcome in the application of PRB technology for remediation of polluted groundwater by uranium is to optimize and evaluate the reactive media. The media employed should provide a long-term sink for metals, and maintain permeability and hydraulic connectivity between the contaminant plume and the reactive treatment zone. Therefore the reactive materials must be more permeable than the natural soil at the site. Also the ow path through the reactive material must be long enough to ensure the reactive zone is sufcient for successful treatment during the ideal period. Many kinds of materials have been employed to form barriers based on several different approaches to the attenuation of the pollutant concentration. The aim of this study is to nd the adsorption performance of uranium (VI) by hematite. Iron is an abundant element and iron oxides are widely distributed in the environment. Iron oxides, especially hematite, which has a large specic surface area and high adsorption capacity, are common components of soil and sediment and are a relatively cheap material compared with other adsorptive materials (Duff and Amrhein, 1996; Martine et al., 2002; Plotnikov and Bannykh, 1997). The adsorption and desorption of iron oxides have been researched by scholars. The aims of this paper were to study the characteristics of hematite as an adsorbent for removing uranium (VI) from aqueous solutions in a batch system, and to investigate its kinetics and thermodynamics. The factors affecting the adsorption efciency include the solution pH, contact time, initial concentration, temperature, and calcium and magnesium ions. It is very important for hematite to be used in PRBs.
2. Materials and methods 2.1. Main instruments PHS-3C precision pH meters, a GB303 electronic balance, HD2-HZQ vertical temperature oscillators, an LEO1450VP scanning electron microscope (SEM), an X-ray diffractometer (D/MAX-2400), and an X-ray uorescence spectrometer (XRF1500) were used in the experiments. 2.2. Materials All of the chemical reagents used in this experiment were analytically pure. Hydrochloric acid and sodium hydroxide were used for pH adjustment. For the preparation of uranyl solutions, 1.2792 g urano uranic oxide solution was put into a 100-ml beaker, and 10 ml hydrochloric acid (specic gravity: 1.19), 8 ml 30% hydrogen dioxide and two drops of nitric acid (specic gravity: 1.42) were added. The beaker was covered and shaken for 3 min. After the reaction had been initiated, the beaker was heated by a sand bath to completely dissolve the solution, and then cooled down. The solution was then transferred to a 1000-ml ask, diluted with water and shaken again to produce the initial uranium (VI) solution with a concentration of 1 g l1. Preparation of synthetical hematite: collosol hematite was hydrolyzed by ferric chloride at 372 K. After 24 h deposition, ltration, water washing and dehydration, collosol hematite was produced. Scanning electron microscopy was used to identify the size of the particles in the hematite, and the specic surface area was tested by the BET method. The results are shown in Table 1. 2.3. Test methods

Table 1 Characteristic parameters of hematite particles. Particle size of hematite Specic surface area Chemical composition (a-Fe2O3) Isoelectric point 0.12 mm 3.4 m2/g >98% 7.6

standard solution vanadiate was used to titrate the solution containing U (VI). These reactions were as follows: UO2D D 2Fe2D D 3H3 PO4 / H2 UPO4 3 D 2Fe3D D 3HD D 2H2 O 2 2Fe2D D NOL D 2HD / FeNO2D D Fe3D D H2 O 2 FeNO2D D NOL D 2HD / Fe3D D 2NO D H2 O 2

NH2 2 CO D 2HD D 2NO2 / 2N2 D CO2 D 3H2 O UHPO4 3 2L D 2VOL D 4HD / UO2D D 2VO2D D 2H2 O D 3HPO4 2L : 3 2 2.4. Batch experiments Bench test: 2 ml U (VI) was transferred into a 100-ml ask and distilled water was added for calibration. A U (VI) solution of 20 mg l1 was obtained. The pH of the U (VI) solution was regulated to range from 3 to 8, and then 0.5 g hematite powder was added into the solution, which was stirred at 150 r/min. The reaction was carried out at the temperature of 293 K for 360 min. After ltration, the concentrations of the solution were obtained by microtitration, and the removal rates could be calculated according to the following equation:  adsorption percentage% Ci Cj Ci 100%: (1)

3. Results and discussion 3.1. Effect of initial pH One of the most critical parameters in the treatment of U (VI) by hematite is the initial pH of the adsorption medium (Prilry1 et al., 1994). The effect of pH on the adsorption capacity of hematite was investigated using solutions of U (VI) when the pH was 3.0, 4.0, 5.0, 6.0 and 7.0 at room temperature. Metal solutions at various initial pHs were adjusted by hydrochloric acid and sodium hydroxide. The effect of pH on the adsorption of uranium by hematite is presented in Fig. 1, which shows that the removal rate is lower when the range
100

80

removal rate/

60

40

20

0
The concentrations of residual U (VI) in the solution were determined with microtitration. Ferrite FeSO4, sodium nitrite and carbamide were added into 35% phosphate medium containing U (VI). Sodium diphenylamine was used as an indicator and

pH
Fig. 1. Effect of initial pH on the removal rate of U (VI) by hematite.

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of pH is between 3 and 4.5, and it increases with the increase of the pH. One or more kinds of U (VI) species could be involved in the adsorption. The distribution ratio could vary with pH. The existence of UO2, (UO2)2(OH)2 and (UO2)3(OH) with the change of pH by 2 2 5 laser Raman spectroscopy was investigated (Bertsch et al., 1994). The results indicated that U (VI) exists in the form of UO2 and its 2 adsorption was weak when the pH was lower than 4. The adsorption efciency of uranium increases observably with the increase of pH. This could be explained by the fact that the increase of (UO2)3(OH) results in the increase of adsorption capacity, and the 5 Coulomb power between (UO2)3(OH) and iron oxides is more than 5 that of UO2. Additionally, the decrease of ionic charge of hydro2 lysate of UO2 could lead to the decrease of secondary solvation 2 energy, thereby improving the adsorption efciency. Other species such as UO2(OH) and (UO2)2(OH)2 exist in the range of pH from 5 2 to 7, but these are not the main forms. 3.2. Effect of removal ratio by interfering ions The concentration of Ca2 and Mg2 in the natural groundwater is about 103 mol l1. In order to reveal the inuence of ferric oxides on adsorption in the presence of Ca2 and Mg2, calcium chloride and magnesium chloride were employed in the suspension solution of hematite. As shown in Fig. 2, the experimental results indicated that Ca2 and Mg2 did not affect the adsorption of uranium by hematite signicantly. 3.3. Morphological characteristics of hematite and X-ray diffraction spectrometry analysis The images of hematite by environmental scanning electron microscopy (ESEM) are shown in Fig. 3 (Powder Metallurgy Research Institute of Central South University, P.R. China). It was obvious that hexagonal crystals and quartet crystals coexisted and were abundant. The hexagonal crystals were a-Fe2O3, the main component of hematite, and the square crystals were magnetic hematite (Fe3O4), the second component. This can also be seen in the X-ray diffraction spectrometry results shown in Fig. 4 (Powder Metallurgy Research Institute of Central South University). The ESEM pictures of hematite after reaction with U (VI) of 80 mg l1 are shown in Fig. 5 (Powder Metallurgy Research Institute of Central South University, P.R. China). In the gure, there are no diffraction peaks of crystals formed by uranium. This may be
100 C(Mg) = 0.001mol/L C(Ca) = 0.001mol/L uranium solution without Ca cation and Mg cation

Fig. 3. ESEM micrograph of hematite.

because the complex formed by U (VI) in neuter solution did not form a crystal lattice after adsorption on the surface of hematite with the function of electrostatic force. 3.4. X-ray uorescence spectrometry analysis The hematite powder after adsorption was dried at a pH of 7, and prepared for X-ray uorescence spectrometry analysis. The contents of all of the different kinds of elements in the powder showed that the content of uranium was equal to the amount of uranium in adsorbed from U (VI) aqueous solution (Table 2). 4. Adsorption isotherm and kinetic analysis 4.1. Adsorption isotherm Adsorption is a well-known equilibrium separation method for wastewater treatment. Adsorption isotherms are the equilibrium relationships between the concentrations of adsorbed elements and elements in a solution at a given temperature. In order to study the adsorption kinetics of hematite, Langmuir equations and Freundlich equations were used to describe the adsorption behavior in solidliquid systems. The expression of the Langmuir model is given by Eq. (2):

80

removal rate/

60 25.0

[5.raw]

Intensity (CPS)

40

20.0 15.0 10.0 5.0 x103

33-0664> Hematite - Fe2O3 25-1402> Maghemite-Q - Fe2O3

20

pH
Fig. 2. Effect of Ca2 and Mg2 on the removal rate of U (VI) by hematite.

2-Theta ()
Fig. 4. ESEM micrograph of hematite having adsorbed U (VI).

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Table 3 Langmuir and Freundlich isotherm constants and correlation coefcients for the adsorption of U (VI). T/K Langmuir model qm/mg g1 293 305 318 3.36 3.46 3.54 Ka 1.01 1.03 1.19 r2 0.9980 0.9989 0.9996 Freundlich model 1/n 0.2672 0.2808 0.2895 Kf 1.56 1.57 1.63 r2 0.8971 0.9042 0.9099

(DS0) can be estimated using the variation of equilibrium constants with temperature. The Gibbs free energy change of the sorption reaction is given as:

DG0 RT ln Ka 2:303RT lg Ka ;

(6)

Hereby R is the universal gas constant (8.314 J mol1 K1) and T is the absolute temperature. According to the equation above, the values of DG0 at the three different temperatures were all below zero and they were 24.24, 74.98 and 460.01 J mol1 respectively. This means that the adsorption processes are spontaneous.
Fig. 5. X-ray diffraction patterns of hematite.

4.2. Kinetics of uranium (VI) adsorbed by hematite

qe qm Ka Ce =1 Ka Ce :

(2)
The pseudo-rst-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model were employed here to describe the kinetic characteristic of uranium (VI) adsorbed by hematite, and the parameters of adsorption kinetic models were calculated. Pseudo-rst-order kinetic model:

The above equation can be transformed into another linear form:

Ce =qe Ce =qm 1=Ka qm ;

(3)

where Ka is the adsorption equilibrium constant; Ce and qe are unadsorbed metal concentrations in solution and adsorbed metal ions on the sorbent at equilibrium respectively; and qm denotes the maximum amount of metal ions per unit weight. The empirical Freundlich equation based on adsorption on a heterogeneous surface is given by Eq. (4):

lgqm qt lg qm K1 t=2:303:
Pseudo-second-order kinetic model:

(7)

qe Kf Ce :

1=n

(4)

Equation (4) can also be transformed into another linear form:

t=qt 1=K2 q2 t=qm : m

Intraparticle diffusion model:

(8)

lg qe lg Kf 1=n lg Ce ;

(5)

qe/ (mg/g)

where qe is the equilibrium metal uptake capacity; Ce denotes the residual metal concentration at equilibrium; and Kf and n are the Freundlich constants related to the adsorption capacity and adsorption intensity of the sorbent respectively. Table 3 shows that the adsorption pattern of uranium by hematite is in accordance with the Langmuir and Freundlich isotherms. Moreover, the data tted the former better than the latter. The initial concentration of uranium (VI) was 20 mg l1. Experiments with the same initial concentration of uranium (VI) were carried out at the temperatures of 293 K, 305 K and 318 K. The adsorption isotherm results are indicated in Fig. 6. In engineering practice, entropy and Gibbs free energy factors should be considered in order to determine what processes will occur spontaneously. Thermodynamic parameters such as enthalpy change (DH0), Gibbs free energy change (DG0) and entropy change

qt Kt t 1=2 C:

(9)

In the models above, K1 (min1), K2 (mg g1 min1) and Kt (mg g1 min1/2) denote the adsorption rate constants respectively; qt (mg g1) is the adsorption capacity in the time of t; and qm and C

4 3.5 3 2.5 2 1.5 1 0.5 0 0 5 10 15 20 25 30 T=293K T=305K T=318K

Table 2 Contents of various elements in the hematite according to X-uorescence spectrum. Elements Contents/% Elements Contents/% Fe 76.3 Al 0.0117 Co 0.106 Si 0.0115 Na 0.0978 Cl 0.0111 U 0.0876 P 0.00748 Mn 0.0205 Cr 0.00665

Ce/ (mg/L)
Fig. 6. Adsorption isotherms at different temperatures on U (VI) adsorbed by hematite.

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Table 4 Kinetic parameters of the adsorption of U (VI) at 293 K. K1 1.13 102 qm 3.82 r1 0.9301 K2 3.66 103 q2 4.1 r2 0.9931 Kt 0.186 C 0.252 rt 0.9798

helpful comments from anonymous reviewers are also gratefully acknowledged. References
Bargar, J.R., Reitmeyer, R., Davis, J.A., 1999. Spectroscopic conrmation of uranium (VI)carbonato adsorption complexes on hematite. Geochimica et Cosmochimica Acta 33, 24812484. Bargar, J.R., Reitmeyer, R., Lenhart, J.J., Davis, J.A., 2000. Characterization of uranium (VI)carbonato complexes on hematite: EXAFS and electrophoretic mobility measurements. Geochimica et Cosmochimica Acta 64, 27372749. Bertsch, P.M., Hunter, D.B., Sutton, S.R., Bajt, S., Bajt, S., Rivers, M.L., 1994. In situ chemical speciation of uranium in soils and sediment by micro X-ray absorption spectroscopy. Environmental Science & Technology 28, 980984. Blowes, D.W., Ptacek, C.J., Benner, S.G., McRae, C.W.T., Bennett, T.A., Puls, R.W., 2000. Treatment of inorganic contaminants using permeable reactive barriers. Journal of Contaminant Hydrology 45, 123137. Catherine, S. Barton, Douglas, I. Stewart, Katherine, Morris, David, E. Bryant, 2004. Performance of three resin-based material for treating uranium-contaminated groundwater within a PRB. Journal of Hazardous Materials B116, 191204. Duff, M.C., Amrhein, C., 1996. Uranium (VI) adsorption on goethite and soil in carbonate solutions. Soil Science Society of America Journal 743, 13931400. Gillham, R.W., Blowes, D.W., Ptacek, C.J., OHannesin, S.F., 1994. Use of zero-valent metals in site remediation of contaminated groundwater. In: Gee, G.W., Wing, N.R. (Eds.), In Situ Remediation: Scientic Basis for Current and Future Technologies. Battelle Press, Columbus, Ohio, USA, pp. 913930. Health Canada, 1999. Uranium in Drinking Water. Document for Public Comment Prepared by Federal Provincial Subcommittee on Drinking Water. Hsi, C.D., Langmiur, D., 1985. Adsorption of uranyl onto ferric oxyhydroxides: application of the surface completion site-binding model. Geochimica et Cosmochimica Acta 49, 19311941. Ma, Teng, Wang, Yanxin, 2000. Coupled reactiontransport modelling of migration of uranium(6) in shallow groundwater system: a case study of uranium gangue site in southern China. Earth Science Journal of China University of Geosciences 25 (5), 456461. Martine, C. Duff, Jessica, Urbanik Coughlin, Douglas, B. Hunter, 2002. Uranium co-precipitation with iron oxide minerals. Geochimica et Cosmochimica Acta 66 (20), 35333547. Ohnuki, T., Isobe, I., Yanase, N., Nagase, N., Nagano, T., Sakamoto, T., Sekine, K., 1997. Change in sorption characteristics of amorphous iron minerals. Journal of Nuclear Science and Technology 34, 11531158. Plotnikov, V.I., Bannykh, V.I., 1997. Sorption of uranium (VI) by metal hydroxides. II. Sorption of uranium (VI) by trivalent metal hydroxides. Radiochemistry 39, 162164. Prilry1, J.D., Pabalan, R.T., Turner, D.R., et al., 1994. Uranium sorption on a-alumina: effects of pH and surface area solutionvolume ratio. Radiochimica Acta 66/67, 291296. Shin, D.C., Kim, Y.S., Moon, J.Y., Park, H.S., Kim, J.Y., Park, S.K., 2002. International trends in risk management of groundwater radionuclides. Journal of Environmental Toxicology 17 (4), 273284. ShuiBo, Xie, Zeang, Chen, Xiaojian, Zhang, et al., 2005. Modeling of migration of the radionuclides in shallow groundwater and uncertainty factors analysis at the uranium mill-tailing site a case study in southern China. In: Proceedings of the ISEIS 2005 Conference, July 26th28th, Xiamen, China, pp. 146152. US EPA, 1999b. National Primary Drinking Water Regulation; Radon-222; Proposed Rule. Waite, T.D., Davis, J.A., Payne, T.E., et al., 1994. Uranium (VI) adsorption of ferrihydrite: application of a surface complexation model. Geochimica et Cosmochimica Acta 58 (24), 54655478. WHO, 1998. Guidelines for Drinking Water Quality. In: Addendum to Volume 2. WHO, Geneva.

are the maximum adsorption capacity (mg g1) and the constant respectively. The relationships of lg(qm qt) to t, t/qt to t and qt to t1/2 were plotted according to the experimental data. All the data were regressed and therefore, K1, K2, Kt, qm, q2, C and the correlative coefcient r were also obtained and are presented in Table 4. The correlative coefcient r of the pseudo-second-order kinetic model was better than those of the other two equations; that is to say, pseudo-second-order kinetic model can be adapted to describe the adsorption process of uranium (VI) by hematite. 5. Conclusions The adsorption of U (VI) in aqueous solution by hematite in a batch system was studied. The results indicated that the adsorption capacity of hematite was affected by the initial pH, temperature and contact time. The removal rate of U (VI) increased with the increasing of pH. The equilibrium adsorption capacity increased with the increase of pH and when the initial pH was around 7, the optimal adsorption effect was gained. The Langmuir and Freundlich adsorption models were used for a mathematical description of the adsorption equilibrium, depending on the temperature, and isotherm constants were used to compare the adsorption capacity of hematite. The comparison revealed that the isotherm constants increased with the increasing of temperature and an increase of temperature could result in a higher loading per unit weight of the sorbent for the U (VI) studied. The results showed that the adsorption equilibrium data tted the Langmuir model in the studied concentration range for all the temperatures studied. The negative value of DG0 conrmed the spontaneous native adsorption process. The correlative coefcient r of the pseudo-second-order kinetic model was better than the others, which conrmed that the pseudo-second-order kinetic model is appropriate to describe the adsorption process of U (VI) by hematite. However, the existence of some dosimetric inference can be assumed from the results, which will be the topic of a forthcoming paper by the authors. Acknowledgements Financial support from the National Natural Science Foundation of China (No. 10775065, No. 20707008) is highly appreciated. The