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Utilization of low-cost sorbent for removal and separation of 134Cs, 60Co and 152+154Eu radionuclides from aqueous solution S. S. Metwally, R. R. Ayoub & H. F. Aly

Journal of Radioanalytical and Nuclear Chemistry An International Journal Dealing with All Aspects and Applications of Nuclear Chemistry ISSN 0236-5731 Volume 302 Number 1 J Radioanal Nucl Chem (2014) 302:441-449 DOI 10.1007/s10967-014-3185-z

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Author's personal copy J Radioanal Nucl Chem (2014) 302:441–449 DOI 10.1007/s10967-014-3185-z

Utilization of low-cost sorbent for removal and separation of 134Cs, 60Co and 152+154Eu radionuclides from aqueous solution S. S. Metwally • R. R. Ayoub • H. F. Aly

Received: 3 March 2014 / Published online: 11 May 2014 Ó Akade´miai Kiado´, Budapest, Hungary 2014

Abstract Eggshell material was used as low-cost and eco-friendly biosorbent for removal of 134Cs, 60Co and 152?154 Eu radionuclides from aqueous solution. The eggshell material was calcined at 500 and 800 °C, and then characterized. Comparative studies on the natural and calcined eggshell for sorption of the three radionuclides were carried out. It was found that, the uptake is in the order: Eu(III) [ Co(II) [Cs(I). Further, column chromatography was used in separation of 134Cs, 60Co and 152?154 Eu using 0.15, 0.2 and 0.5 mol/l nitric acid, respectively. Eggshell material can be considered as a promising material for separation of radionuclides from radioactive waste solution. Keywords

Eggshell  Sorption  Column  Separation

Introduction Environmental and health issues caused by radioactive waste have drawn increasing attention around the world since the extensive application of nuclear energy started from the early stages of the 20th century [1]. In Egypt, low and intermediate level radioactive wastes are

Electronic supplementary material The online version of this article (doi:10.1007/s10967-014-3185-z) contains supplementary material, which is available to authorized users. S. S. Metwally (&)  R. R. Ayoub  H. F. Aly Hot Laboratories Center, Atomic Energy Authority, Cairo 13759, Egypt e-mail: [email protected]

produced during research activities of the radiochemical laboratories, research reactors, radioisotope and metallurgical laboratories, activation analysis units, nuclear medicine divisions in hospitals as well as industrial activities [2]. These wastes arise in a wide range of concentrations of radioactive materials and a variety of physical and chemical forms. Among these are the radioactive nuclides 134Cs, 60Co and 152?154Eu. Release of these radionuclides from solutions of low level radioactive waste disposal facilities on the environment cannot be totally excluded with subsequent contamination for water and soils [3]. 60 Co is a corrosion product which presents in the cooling water of reactors [4]. The exposure to high concentrations of cobalt may cause sterility, hair loss, vomiting, bleeding, diarrhea, coma and even death. 134 Cs is a fission product radionuclide and often presents in low level radioactive waste solutions produced from different research activities. Cesium radioisotopes, 134 Cs and 137Cs, can be easily incorporated into terrestrial and aquatic organisms because of its similar chemical characteristics with sodium and potassium [5]. Therefore, ingestion of these radioisotopes results in their deposition in the soft tissues all over the body creating an internal hazard, especially to the reproductive system [6]. Hence, the radioactive wastes which contain cesium must be adequately treated prior to discharge to the environment. 152,154 Eu isotopes are produced primarily as fission products [7]. It can also be produced by neutron activation of nuclear reactor control rods [8]. Therefore, it is found in certain places, around nuclear reactors and facilities that process spent nuclear fuel. There is a variety of methods in the treatment and conditioning of wastes prior to disposal. The selection as

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a treatment process for an aqueous waste is determined by the physical, chemical and radiological properties of the waste. The processing of liquid waste aims to separation of the radionuclides from the liquid phase and concentrating them in a solid waste form. The separation is pursued until the residual concentration or total amount of radionuclides in liquid phase is below the limits set by the regulatory body for the discharge of liquid waste from a nuclear facility as an effluent. The treatment technologies employed in nuclear industry include chemical precipitation [9], ion exchange [10], membrane processes [11], solvent extraction [12] and biotechnology [13]. The sorption process, which includes metal immobilization in contaminated water, has gained attention in the past few decades due to its advantages such as high efficiency, low operating cost and it is ecofriendly when compared to conventional treatment methods [14, 15]. Several researchers have explored different types of sorbents for treating radioactive wastes to get rid of accumulated radioactive contaminants [16, 17]. The aim of research in present days is to protect the environment, not by cleaning up, but by designing new chemicals or biochemical processes benign to the environment. Green chemistry emphasizes renewable starting materials for better economy using biological materials. Nowadays, the use of hazardous chemicals is being restricted, and greener alternatives are gaining importance as replacements. Development of cost effective alternative technologies, such as use of biological reagents for desired chemical processes have become an intensive area of exploitation over the past decade. Waste eggshells contain high contents of calcium carbonate (85–95 %) [18]; therefore, their recycling or reuse has the potential to reduce environmental pollution while acting as a cost effective material for the immobilization of heavy metals in wastewater and soil. Eggshell material was used in various applications as an adsorbent [19], membrane [20] and immobilization supports [21]. The present work aims to evaluate the performance of natural and calcined eggshell, as biosorbents, for removal of radioisotopes, 134Cs, 152,154Eu and 60Co, as a green method for isolation of these radionuclides from aqueous solution.

Experimental Chemicals All chemicals and reagents used in this study were of analytical grade purity and were used without further

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purification. Cobalt nitrate was purchased from Merck, cesium and europium nitrate were obtained from Aldrich Chem. Co. The pH was adjusted by the addition of NH4OH or HCl which obtained from Fluka. 152?154Eu, 60Co and 134Cs isotopes were prepared by irradiating the salts in the second Egyptian Research Reactor, ERR2, at the Inshas site. For all experiments double distilled water was used. Aqueous solutions, 10-3 mol/l, of cesium, cobalt and europium ions were prepared by dissolving known quantities of salts of the three metal ions in double distilled water, which were labeled with 134Cs, 60Co and 152,154Eu isotopes, respectively, and kept as stock radioactive solutions for further use. White chicken eggshell material is widely produced from house and restaurants. The inner shell membrane and the limiting membrane were manually removed. To remove impurity and salts, a sample of eggshell was rinsed several times with deionized water. Then, the sample was dried at 90 ± 1 °C for 24 h in the dry oven. Calcination was performed in the furnace at 500 and 800 °C for 2 h after crushing the dried sample. Characterization of the eggshell material X-ray diffraction spectra of natural and calcined eggshell were made using an X-ray powder diffractometer (Philips Analytical PW-1710) equipped with Cu Ka radiation at a scanning speed of 2°/min from 10° to 90° operated at voltage 40 kV and applied potential current 30 mA. FTIR has been used for the examination of functional groups of the natural and calcined eggshell. To obtain the observable absorption spectra, homogenization of the dried samples with KBr, spectroscopic grade, was carried out with additional grinding and mixing in an agate mortar. Disks were prepared in a manual hydraulic press (Perkin Elmer Co., USA) at about 10 ton. The spectrum was measured and recorded (500–4,000/cm) on a spectrometer model system 2000 FTIR, Perkin Elmer Co., USA. Surface area, pore volume and pore size distribution of the natural eggshell and calcined eggshell were determined from nitrogen adsorption data at -196 °C which was conducted using a gas sorption analyzer, Quantachrome, NOVA 1000e series, USA. In order to characterize calcinations of eggshell, thermal gravimetric analyzer, Shimadzu DTA–TGA system of type DTA-TGA-50, Japan was used for the measurements of the phase changes and weight losses of the sample. A portion of the dried eggshell previously removed impurity and interference material was loaded in the TGA analyzer and then pyrolysis was performed up to 1000 °C at an

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elevation of temperature 40 °C/min with continuous injection of N2. Adsorption experiments As pH is one of the governing factors in the biological system, first the uptake of these elements by eggshell was studied as a function of pH keeping other parameters fixed. For the study of the variation in metal uptake with pH, 5 ± 0.1 ml of metal ion solution of required pH, adjusted with diluted HCl or NaOH, were shaken for 180 min with 0.1 ± 0.002 g of eggshell. The initial and final activities, A0 and A respectively, of different radioisotopes were measured using a high resolution NaI(Tl) c-ray spectrometry model 802-3X3 with pulse height multi-channel analyzer (McA), Canberra, USA. The percent uptake can be calculated by the following formula: % Uptake ¼

A  Ao  100: Ao

ð1Þ

A batch technique was followed to determine the percent uptake at different times where 0.1 g of the eggshell was shaken at 25 ± 1 °C with 5 ml of 10-3 mol/l of each of Cs(I), Co(II) and Eu(III) ions, labeled with 134Cs, 60Co and 152?154Eu, respectively. The pH was maintained at which maximum percent uptake was obtained as indicated from the previous results. After an overnight standing (sufficient to attain equilibrium) the mixtures were centrifuged and the percent uptake was determined as mentioned above. The capacities of natural and calcined eggshell materials were determined by the repeated batch technique. Equilibrating 0.1 g of each with 10 ml of 0.01 mol/l Cs(I), Co(II) and/or Eu(III) solutions labeled with 134Cs, 60Co, and 152-154 Eu on a shaker at room temperature. After equilibrium, the liquid and the solid phases were separated and then the activity of each isotope was measured in the liquid phase to calculate the percent uptake, Eq. (1). The process was repeated until saturation where no further sorption occurs. The capacity, meq/g, was calculated using the following equation [22, 23]: P V % Uptake Capacity ¼ ð2Þ  Co  Z  ; m 100

used in the experiments was 6 ± 0.1 cm. The sorbent was temped through the column after incorporation of thickness 2 mm glass wool disc in the bottom of the column and over the top of the bed. The loading process was carried out by passing an appropriate volume of the solution containing 50 ± 1 mg/l of Cs(I), Co(II) and Eu(III) ions labeled with 134 Cs, 60Co and 152?154Eu through the column bed at a flow rate of 0.5 ± 0.01 ml/min and pH 6 ± 0.2. Then the separation of the three radionuclides was carried out at the same flow rate and bed depth by using different nitric acid molarities.

Results and discussion Characterization of natural and calcined eggshell Figure 1 shows powder XRD pattern for natural and calcined eggshell. For natural eggshell, a main peak appeared at 2h = 29 as well as several peaks as illustrated in the figure. Comparing the XRD peak information with JCPDS file, the peaks are well matched with that of calcite (CaCO3). While for calcined eggshell at 500 and 800 °C, the main peak appeared at 2h = 37.5 and other peaks appeared. These peaks are well matched with that of CaO. The changes in the observed pattern of natural and calcined eggshell due to transformation of calcium carbonate, CaCO3, into calcium oxide, CaO, producing also carbon dioxide as illustrated by Eq. (3) [24]. The increasing of temperature, from 500 to 800 °C leads to increase of release of CO2 and formation of

where Co is the initial concentrations of the tested ion, mmol/l, V is the volume of solution, in litter, m is the weight of material, in gram and Z is the charge of metal ion. Column technique The fixed bed column was made of Perspex column of 1 cm inner diameter and 20 cm height. The bed length

Fig. 1 XRD pattern for a natural eggshell, b calcined eggshell at 500 °C and c calcined eggshell at 800 °C

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CaO. The peak of CaCO3 (2h = 29) disappeared in the spectrum of the calcined eggshell at 800 °C, this indicates that most of CaCO3 might be transformed into CaO as presented in the following equation: Calcination

CaCO3  ! CaO þ CO2 "

ð3Þ

FT-IR spectra of natural and calcined eggshell are given in Fig. 2. One main characteristic peak for natural eggshell, Fig. 2a, was observed at 1417.48, which confirmed the presence of calcite, CaCO3 [25]. The weak band at 1797.5/ cm corresponds to C=O from carbonate, while the band at 874/cm are characteristic of the C–O of calcium carbonate and the sharp band at 710.5/cm is related to Ca–O bonds [26]. The broad band at 3403.4/cm is attributed to OH stretching vibration from residual water. Figure 2b shows the spectrum of the calcined eggshell at 500 °C. It is found that the band at 710.5/cm characterized for Ca–O bond is still present. The existence of peak at 3,636/cm is due to OH in Ca(OH)2 formed during adsorption of water by CaO [26]. The sharpness of the characteristic band of CaCO3, at 1,417/ cm, decreased while that of CaO, at 710.5/cm, increased due to transformation of a part of CaO3 into CaO. For Fig. 2c the bands of CaO3, C=O and C–O disappeared, this indicates that most of CaCO3 might be transformed into CaO. TGA pattern of natural eggshell is presented in Fig. 3. Two distinct stages of weight losses were obtained, the first stage below 400 °C can be attributed to water release and loss of organic compounds. The second stage exhibited the major weight loss at 790 °C, corresponding to 45 wt% due to the transformation of CaCO3–CaO which could be confirmed by the XRD and the FTIR results (Figs. 1, 2). The sample weight remained constant after 790 °C, therefore, the temperature of 800 °C is suitable to the use as the calcination temperature to ensure complete conversion to CaO. The DTA line indicated that the eggshell is characterized by endothermic peak. Surface area (SBET), average particle size, total pore volume (Vtotal), micropore volume (Vmicro) and mesopore volume (Vmeso) of natural and calcined eggshell were determined as illustrated in Table 1. This table indicates that they increased with increasing the calcinations temperature.

Fig. 2 FT-IR spectra of a natural eggshell, b calcined eggshell at 500 °C and c calcined eggshell at 800 °C

Effect of pH

Fig. 3 TGA–DTA pattern of natural eggshell

The initial pH of the solution is an important parameter which controls the sorption process. It affects on the surface of the adsorbent and the chemistry of metal ion in solution. The effect of pH on percent uptake of the three radionuclides, 134Cs, 60Co and 152?154Eu, onto natural and calcined eggshell was studied in the pH range 2–9, while for Eu the pH range was only 2–6 to avoid complications from precipitation of europium at higher pH, in aqueous

solution, the hydrolysis of trivalent europium begins at pH as low as 6 and various species can be formed [27]. Figure 4 clearly illustrates that % uptake of the studied radionuclides increases with increasing pH. The low degree of uptake of the three radionuclides at low pH values, 2–4, can be explained by the fact that at low pH the hydrogen ion concentration is high, therefore, the net charge on the

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Table 1 Surface area, particle size, pore volume and pore size distribution of natural and calcined eggshell Property

Particle size (lm) 3

Natural eggshell

Calcined eggshell at 500 °C

Calcined eggshell at 800 °C

21

13

8

3

Vmeso 9 10 (cm /g)

1.3

2.7

4.3

Vmicro 9 105 (cm3/g)

8.8

106

201

Vtotal 9 103 (cm3/g)

2.6

4.6

6.3

SBET (m2/g)

1.7

9.9

15.3

sorbent surface is positive which inhibits the approach of positively charged species. In addition, as pH increases, surface positive charge decreases. Higher % uptake was obtained in case of calcined eggshell at 800 °C than that of calcined eggshell at 500 °C which is greater than that of natural eggshell, this sequence

is resulting from the presence of CaO with high quantity in calcined eggshell at 800 °C which is characterized by high surface area and high pore volume which enhance the % uptake. From Fig. 4 it was found that, the percents uptake for 134Cs, 60Co and 152?154Eu radionuclides were increased with increasing pH and the selectivity sequence is in the order: Eu(III) [ Co(II) [ Cs(I). This may be due to the increase of electrostatic interaction of the multivalent cation compared to the monovalent one [24]. The speciation of cesium, cobalt and europium ions in aqueous solution is shown in Fig. 5. It was performed with the visual MINTEQA computer program version 3.0 [28] at 10-5 mol/l initial metal ion concentration, ionic strength of 0.01, room temperature and pH range 2–9 for Cs(I) and Co(II) and pH range 2–6 for Eu(III) ions. From the speciation diagram (Fig. 5a), Cs(I) is the predominant species at all studied pH range. Whereas cobalt is presented mainly as Co(II) till pH 5, after which Co(OH)? is appeared, and at pH 7.2–9 Co(OH)2 is presented as shown in Fig. 5b.

Fig. 4 Effect of pH on % uptake of 134Cs, 60Co and 152?154 Eu radionuclides onto different types of eggshell

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While for europium ions, Eu(III) is the predominant ion till pH 4 and Eu(OH)2? appears at pH 4–6 as presented in Fig. 5c. Effect of contact time

Fig. 5 Speciation of a Cs?, b Co2? and c Eu3? at different pH Fig. 6 Effect of contact time on % uptake of 134Cs, 60Co and 152?154 Eu radionuclides onto different types of eggshell

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In order to interpret the experimental data, it is necessary to determine the step that governs the overall removal rate for the sorption process, which is actually a sequence of steps: (1) transport of the sorbate from the fluid to the external surface of the sorbent across the boundary layer (film diffusion), (2) diffusion of the sorbate within the pores of the sorbent (particle diffusion) and (3) sorption itself onto the surface. Out of these, the third process is considered as very fast and cannot be treated as a rate determining step for the uptake of the three radionuclides. For the other two steps, the following three possibilities remain: (case 1) external transport [ internal transport, where the rate is governed by a particle diffusion, (case 2) external transport \ internal transport, where the rate is governed by a film diffusion, (case 3) external transport = internal transport, the

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transport of sorbate to the boundary may not be possible at a significant rate leading to the formation of a liquid film having a concentration gradient surrounding the sorbent particles [29], but the third case may be excluded. The effect of contact time on the sorption of 134Cs, 60Co and 152?154 Eu by natural and calcined eggshell was investigated over the time intervals of 3–180 min as shown in Fig. 6. Maximum % uptake of 36 ± 1, 50 ± 1 and 81 ± 2 % for sorption of 134Cs onto natural eggshell, calcined eggshell at 500 °C and calcined eggshell at 800 °C, respectively, were obtained at equilibrium. While 43 ± 1, 52 ± 1 and 85 ± 2 % were obtained for sorption of 60Co onto the same three sorbents, respectively, and 50 ± 1, 57 ± 1 and 92 ± 2 % for sorption of 152?154Eu. During the initial stages of the sorption process, sorption rate was rapid, after which, uptake rate slowly declined and tended to attain equilibrium at 180 ± 3 min. It can be hypothesized that during the initial stages of the sorption process, the higher concentration of the three ions provide the driving force to facilitate ion diffusion from solution to the active sites of the sorbent. As the process continues, occupation of the active sites and the decrease of the metal ions concentration, leads to a decrease in uptake rate until equilibrium is achieved [30].

Column technique The loading behavior of Cs(I), Co(II) and Eu(III) ions sorbed onto the calcined eggshell in a fixed bed for a fixed flow rate of 0.5 ml/min and initial metal ion concentration of 50 ± 1 mg/l are shown by breakthrough curve between concentration ratio, Ct/C0, and effluent volume, Fig. 7. Equilibrium metal uptake (qeq) (or maximum capacity of the column) in the column is defined as: the total amount of metal sorbed (qtot) per g of sorbent (w) at the end of total flow time as illustrated by the following equation [31]: qtot : ð4Þ qeq ¼ W The total amount of metal sorbed (qtot, mg) in the column for a given feed concentration (C0, mg/l), flow rate (Q, ml/min) and total flow time (ttot, min) can be found by calculating the area under the breakthrough curve (A) obtained by integrating the sorbed ion concentration (Cads, mg/l) versus time plot as the following equation [32]:

Determination of capacity The capacities of Cs(I), Co(II) and Eu(III) ions on the natural and calcined eggshell were determined and illustrated in Table 2. The data shows that the calcined eggshell at 800 °C has the highest capacity. This is resulting from the presence of CaO with high quantity in calcined eggshell at 800 °C which is characterized by high surface area and high pore volume which enhance the capacity. And the selectivity sequence is in the order: Eu(III) [ Co(II) [ Cs(I), this may be attributed to that the multivalent ions have greater complexing ability than the divalent and monovalent ions [4]. The results illustrated that the three isotopes have higher percent uptake values in case of calcined eggshell at 800 °C, therefore, the column studies are tested for sorption onto this type of eggshell. Fig. 7 Breakthrough curve for sorption of Cs(I), Co(II) and Eu(III) ions onto calcined eggshell Table 2 Capacities of Cs?, Co2? and Eu3? ions on natural and calcined eggshell Metal ion

Cs

?

Co2? Eu3?

Capacity (meq/g)

Table 3 Fixed bed data for sorption of Cs?, Co2? and Eu3? ions onto calcined eggshell Metal ion

qeq (mg/g)

qtot (mg)

mtot (mg)

Total ion removal (%)

Cs?

10.8

21.5

39.9

53.8

2.23 ± 0.04

Co2?

11.7

23.4

34.5

67.8

2.99 ± 0.05 4.12 ± 0.08

Eu3?

13

26

28.9

89.9

Natural eggshell

Calcined eggshell at 500 °C

Calcined eggshell at 800 °C

1.71 ± 0.03

1.98 ± 0.04

2.11 ± 0.04 3.19 ± 0.06

2.54 ± 0.05 3.45 ± 0.07

The uncertainty of the measurement was 2 %

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qtot

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QA Q ¼ ¼ 1,000 1,000

t¼t Z tot

Ztot

Q Cads dt ¼ 1,000

t¼0

ðCo  Ct Þdt:

Table 4 Comparison of the sorption capacities of Cs?, Co2? and Eu3? ions on natural and synthetic sorbents Sorbent

0

Capacity (meq/g)

ð5Þ The total amount of ion fed to the column (mtot, mg) is calculated from the following equation [31, 32]: mtot ¼ Co

Veff ; 1,000

ð6Þ

where Veff is the volume of the effluent, ml, which equals: Veff = Q ttot. The total ion removal, %, by the column i.e. the column performance can be calculated from the following equation: qtot Total ion removal ð%Þ ¼  100: ð7Þ mtot The maximum capacity of the column and the percent removal (column performance) of Cs(I), Co(II) and Eu(III) ions are illustrated in Table 3. It is observed that the obtained capacities are less than those obtained from batch experiments, this behavior could be attributed to the insufficient time required for equilibrium in case of column operation. Figure 8 represents the separation of 134Cs, 60Co and 152?154 Eu radionuclides loaded on calcined eggshell. The loading process was carried out by passing an appropriate volume of a solution mixture of the three radionuclides. By

Cs

?

Co

2?

Eu

Reference 3?

Calcined eggshell, 800 °C

2.23

2.99

4.12

Present work

Chitosan derivatives



0.99

0.68

[3]

PAM-CPa Ce(IV) antimonite

2.82 1.19

3.74 0.57

4.23 –

[33] [34]

KCNF-PANb

2.85

4.30



[35]

R-F exchanger

c

6.37

1.66

2.86

[22]

ZMPPd

3.92

2.15

2.67

[22]

Magneso-silicate

0.57

1.16



[23]

Magnesium alumino-silicate

0.77

1.00



[23]

a

Refers to polyacrylamide based Ce(IV) phosphate

b

Refers to potassium hexacyanoferrate–polyacrylonitrile

c

Refers to resorcinol–formaldhyde

d

Refers to zirconyl molybdopyrophosphate

using bidistilled water, 0.01 and 0.1 mol/l nitric acid as eluents, no release of any of the radionuclides was observed; therefore, different nitric acid molarities were used. The first stage is an elution by 0.15 mol/l HNO3 with flow rate 0.5 ml/min to separate 134Cs radionuclide. The next stage is an elution by 0.2 mol/l HNO3 with the same flow rate to separate 60Co radionuclide. Then the last stage is the separation of 152?154Eu by elution using 0.5 mol/l HNO3. Table 4 represents a comparison of the sorption capacities of Cs(I), Co(II) and Eu(III) ions on eggshell, natural and synthetic sorbents. It illustrates that eggshell material can be considered as a promising material for removal of the three metal ions, even compared to some other low cost sorbents previously suggested for the removal of Cs(I), Co(II) and Eu(III) ions from aqueous solutions [3, 22, 23, 33–35].

Conclusion

Fig. 8 Separation of 0.5 ml/min flow rate

123

134

Cs,

60

Co and

152?154

Eu radionuclides at

Eggshell material was successfully calcined at 500 and 800 °C and used for removal and separation of 134Cs, 60Co and 152?154Eu radionuclides. The calcination process transformed the calcite, CaCO3, into CaO. Higher % uptake was obtained in case of calcined eggshell at 800 °C than that of calcined eggshell at 500 °C which is greater than that of natural eggshell, this sequence is resulting from the presence of CaO with high quantity in calcined eggshell at 800 °C which characterized by high surface area and high pore volume, which enhance the % uptake. The increase of pH values enhanced the % uptake, the selectivity sequence is in the order: Eu(III) [ Co(II) [ Cs(I). Column chromatography was used for separation of the three radionuclides. 134Cs,

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Co and 152?154Eu were separated from each other using 0.15, 0.2 and 0.5 mol/l nitric acid respectively.

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