Results in Materials 8 (2020) 100138

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Results in Materials
journal homepage: www.journals.elsevier.com/results-in-materials

Synthesis and characterization of core-shell magnetite nanoparticles with

modified nano-cellulose for removal of radioactive ions from
aqueous solutions
H.M.Abd Elrhman
Physics and Chemistry Department, Faculty of Education, Alexandria University, P. O. Box 21526, El-Shatby, Alexandria, Egypt

A R T I C L E I N F O A B S T R A C T

Keywords: Core-shell superparamagnetic magnetite nanoparticles material with nano-cellulose and modified nano-cellulose
Magnetite (as nano-cellulose citrate, nano-cellulose carbmate and nano-cellulose acrylamide graft) were synthesized using
Nano-particles chemical method. The samples were characterized by Transmission Electron Microscopy (TEM), X-ray Diffraction
Nano-cellulose
(XRD), Fourier Transformed Infrared Spectroscopy (FTIR) and Vibration Sample Magnetometer (VSM). Solid
Core-shell
232
Th daughters
phase extraction (SPE) technique was used to extract the Th232 daughters from aqueous solution using samples.
Adsorption capacity The extraction efficiencies of samples were investigated by measuring the activity of radioactive ions before and
Activity after treatment using High resolution gamma rays spectrometer of hyper pure germanium detector. The effects of
type of sorbent, contact time, pH, initial concentrations of adsorbate, adsorption kinetics and adsorption iso-
therms in one average thickness shell were investigated. The present work study shows that the coating of nano-
magnetite with modified nano-cellulose enhanced the adsorption process especially nano-cellulose citrate. Using
modified nano-cellulose as coating for Fe3O4 gives economic feasibility, which is to be used in water treatment
due to the low cost of production, zero toxicity and suitability to apply to a large volume of solution.

1. Introduction
Thorium is the most abundant radioactive element and is commonly
used in various fields, such as optic, radio, aeronautical, chemical and
material industries.232Th, 238U, 226Ra, and their radioactive daughters
are the most radionuclides present in the environment. Sometimes their
levels in drinking water are high and represent radiological health
problems. Therefore, treatment of such water will be necessary for ra-
diation protection. Unfortunately, 232Th (T1/2 14.1E9 years) is the most
abundant thorium isotope (99%) in the environment. 232Th and the other
members of its decay chain as shown in (Table 1) not only have radio-
toxicity but also have chemotoxicity which can cause a large scale per-
manent damage in bone, kidney, and liver [2].
In the environment, 232Th exists in various combinations with other
minerals, such as silica. Most its compounds found in the environment
are not readily dissolved in water and evaporated in air from the soil or
liquid. Due to its longer half-life it extremely slows rate of decay;
therefore, the total amount of natural thorium in the earth remains
almost the same. 232Th or its compounds can be moved from place to
place by nature and become a part of the soil and when it rains, the
thorium-containing soil can be washed into rivers and lakes [3].
228
Ra (half-life 5.7 years) is one of the important member of 232Th
decay series and is chemically active, so it moves easily in the environ-
ment. In addition, due to the high solubility of radium salts in water it has
high mobility in aquifer water. To protect general public against radia-
tion, World Health Organization (WHO) set a limit for radium-228 in
water (0.1 Bq/L) to be suitable for drinking [4].
The gamma emitter daughters of radium are 228Ac (6.1 h), 212Pb (16.6
h), 212Bi (61min) and 208Tl (3.1min) are highly radioactive and generate
in water. Worldwide attention is paid to the treatment of radioactive
contaminants in drinking water due to the recognition of its importance
for the protection of human health and the environment from the adverse
effects of radiation associated with such wastes [5]. Several technologies
for removing radiological contaminants from drinking water are
considered safe for human health [6].
Solid phase extraction (SPE) is one of the most effective recovery/
removal methods due to its simplicity, low cost and broad adaptability. In
SPE, the sorbent is a key factor in the search for new sorbents with a high
surface area, fast sorption kinetics and good stability at a wide pH range.
Recently, magnetic nano-particles (MNPs), especially Fe3O4 attracted
increasing attention due to its excellent features, such as easy separation
and low toxicity. Moreover, MNPs are susceptible to air oxidation and

E-mail address: hmmam_8080@yahoo.com.

https://doi.org/10.1016/j.rinma.2020.100138
Received in revised form 30 July 2020; Accepted 20 August 2020
Available online 28 August 2020
2590-048X/© 2020 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
H.M.Abd Elrhman Results in Materials 8 (2020) 100138

Table 1 cellulose were selected as intrinsic absorbents. Magnetite nanoparticles

232
Th decay series with half-life and type of decay emission [1]. were coated with nano-cellulose whish added more adsorption features.
Isotope Half-life Decay Functionalization of nano-cellulose (as nano-cellulose citrate, nano-
cellulose carbmate and nano-cellulose acrylamide graft) enhanced the
232
Th 1.40Eþ10 years α
228
Ra 5.80Eþ00 years β adsorption capacity for adsorbents to adsorb Th232 daughters (228Ac,
212
228
Ac 6.10Eþ00 h β Pb, 212Bi and 208Tl radioisotopes) from aqueous solutions by
228
Th 1.90Eþ00 years α measuring the activity of radioactive ions before and after treatment
224
Ra 3.60Eþ00 days α using High resolution gamma rays spectrometer of hyper pure germa-
220
Rn 5.50Eþ01 s α
216
Po 1.50E-01 s α
nium detector. Then, the capability of removing the radioactive ions was
212
Pb 1.06Eþ01 h β evaluated. The effects of type of sorbent, contact time, pH, initial con-
212
Bi 6.10Eþ01 min β,α centrations of adsorbate, adsorption kinetics and adsorption isotherms
212
Po 3.00E-01 s α were investigated.
208
Tl 3.00Eþ00 min β
208
Pb stable –
2. Materials and methods

leaching under acidic conditions. They are also easily aggregated into
aqueous solutions due to anisotropic dipolar attraction, which reduces
the sorption capacity and the application range of it [7].
Magnetic polymer nanoparticles are usually composed of a magnetic
core surrounded by a polymer shell to overcome the reduction of sorption
capacity. The magnetic part is often magnetite nanoparticles while
polymer shell is composed of polymers [8] as Chitosan for removal of
radionuclide Sr2þ and other ions from aqueous solutions [9,10]. It is
favorable to add a function group on the polymer shell to enhance its
adsorption effectiveness, where the function group can react with
different metallic species through the mechanism of chelating and/or
ion-exchange [11]. Magnetically responsive cellulose materials are spe-
cial materials, in which magnetic nano-particles are embedded in the
polymer matrix [12].
Cellulose is a polysaccharide polymer which consists with hundreds
linear chain of linked D-glucose units as a formula (C6H10O5)n. It pos-
sesses good physical and chemical properties as colorless, odorless,
nontoxic, mechanical strength, biocompatibility, hydrophilicity, relative
thermo-stabilization, high sorption capacity, and alterable optical
appearance [13]. Cellulosic nano-particles, generally known as
nano-cellulose, have garnered interest from the scientific community
because of their biodegradability, strength, and other characteristics. It
can be prepared by a mechanical treatment or acid hydrolysis of cellu-
losic biomass [14]. The chemical modification of cellulose can be
enhanced via the extraction efficiency to adsorb heavy metal of un-
modified cellulose [15].
In the present study, magnetite nanoparticles (Fe3O4) and nano-
2.1. Materials
Cellulose powder (C6H10O5)n pH ¼ 5:7 purchased from (Labache-
mie), Ferrous Chloride tetrahydrate FeCl2⋅4H2O (Sigma Aldrich), Ferric
Chloride hexahydrate FeCl3⋅6H2O (Sigma Aldrich), Sodium hydroxyl
NaOH, Citric acid monohydrate C6H10O8, Urea CH4N2O, Acrylamide
C3H5NO, N,N-Dimethylformamide DMF (Sigma Aldrich), Ethanol abso-
lute C2H5–OH (Sigma Aldrich), Acetone and Thorium Chloride ThCl4
56%.
2.2. Preparation of modified cellulose
2.2.1. Cellulose citrate
Cellulose powder (C6H10O5)n (1 g) with Citric acid anhydride(3 g)
(prepared by heating Citric acid monohydrate in oven for 24 h at 100̊c
then was put after cooling in desiccators with desiccant Copper(II) sul-
phate anhydrous to avoid the moisture) and DMF(15 ml) as a solvent are
refluxed for 8 h at 180̊c and stirred with magnetic stirrer. Then the
product was filtrated under vacuum and washed with distilled water and
acetone several times then dried at room temperature.
2.2.2. Cellulose carbamate
1 g of Cellulose powder (C6H10O5)n with (3 g) urea or acrylamide and
DMF(15 ml) at the same conditions of previous reaction were applied.
2.2.3. Cellulose - acrylamide graft
(1 g) Cellulose powder (C6H10O5)n with (3 g) acrylamide and DMF(15
ml) at the same conditions of previous reaction were applied.

Fig. 1. TEM images of (a) Fe3O4 and (b) Fe3O4 @Nano-cellulose.

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H.M.Abd Elrhman Results in Materials 8 (2020) 100138

Fig. 3. FT- IR patterns of (a) Nano-cellulose; (b) Cellulose citrate; (c) Cellulose
carbamate; (d) Cellulose - acrylamide graft.

Fig. 2. XRD patterns of (a) nano-cellulose (b) Fe3O4 (c) Fe3O4 @nano-cellulose
citrate (d) Fe3O4 @nano-cellulose carbamate and (f) Fe3O4 @nano-cellulose -
acrylamide graft.

Table 2
The calculated crystal size and lattice strain calculations.
Material Crystal size (nm) strain

Nano-cellulose 9.931 0.00992

Fig. 4. FT-IR of (a) Fe3O4 (b) Fe3O4@nano-cellulose (c) Fe3O4@nano-cellulose
Fe3O4 13.053 0.00200
Fe3O4 @Nano-cellulose 25.381 0.00002
carbamate (d) Fe3O4@nano-cellulose- acrylamid graft.
Fe3O4 @Nano-cellulose citrate 37.043 0.00120
Fe3O4 @Nano-cellulose carbamate 44.500 0.00765
Fe3O4 @Nano-cellulose - acrylamide graft 41.533 0.03675 precipitation method with FeCl3⋅6H2O and FeCl2⋅4H2O according to
[16].
2.2.4. Preparation of nano-cellulose
2.2.6. Preparation of nano-cellulose coated Fe3O4 (Fe3O4@nano-cellulose)
Cellulose powder (2 g) was dissolved in 15 ml (2 H2SO4 56%:1
2 g of cellulose powder was dissolved in 15 ml (2 H2SO4 56%:1
Glycerol) to form suspension. Then neutralized with NaOH(1N) to form
Glycerol) then mixed with solutions of 0.025mol from FeCl3⋅6H2O in 25
the precipitation followed by washing with distilled water and finally
mL of distilled water and 0.0125mol of FeCl2⋅4H2O in 25 ml of distilled
drying at room temperature.
water under high rate of magnetic stirrer at 50̊c then were applied the
same conditions of previous reaction.
2.2.5. Preparation of Fe3O4 nano-particles
The Fe3O4 nano-particles were synthesized via a chemical Co-

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H.M.Abd Elrhman Results in Materials 8 (2020) 100138

Fig. 5. Shows magnetic hystrysise loops for prepared samples at room temperature.

2.2.8. Preparation of nano-cellulose carbamate coated Fe3O4 (Fe3O4

Table 3
@nano-cellulose carbamate)
Shows the magnetic parameters deduced from hystrysise loops for prepared
1 g of Fe3O4 @nano-cellulose and 2.49 g of urea were added to 25 ml
samples at room temperature.
of ethanol absolute under the same conditions of previous reaction.
Material Ms (amu/g) Mr (amu/g) Hc (G)

Fe3O4 56.605 0.18240 3.9553 2.2.9. Preparation of nano-cellulose-acrylamide graft coated Fe3O4 (Fe3O4
Fe3O4 @Nano-cellulose 36.711 0.18514 5.1311 @nano-cellulose- acrylamide graft)
Fe3O4 @Nano-cellulose citrate 34.635 0.075.609 2.1644
Fe3O4 @Nano-cellulose carbamate 36.028 0.76981 26.804
1 g of Fe3O4 @Nano-cellulose and 2.49 g of acrylamide were added to
Fe3O4 @Nano-cellulose - acrylamide graft 35.654 0.93383 31.866 25 ml of ethanol absolute under the same conditions of previous reaction.

2.2.7. Preparation of nano-cellulose citrate coated Fe3O4 (Fe3O4 @nano-
cellulose citrate)
1 g of Fe3O4@nano-cellulose with 2.49 g of citric acid anhydrate were
added to 25 ml of ethanol absolute then refluxed at 80̊c for 8hrs. The
obtained precipitation was filtrated under vacuum then washed with
ethanol absolute several times then dried at room temperature for 24 h.
2.3. Characterization
TEM images were performed by Jeol.Jem-100cx electron microscope.
XRD patterns of all samples were recorded by (Bruker Germany) super X-
ray diffractometer, FT-IR spectra were recorded by vertex 70 FT-IR
spectrophotometer, and Magnetic hysteresis loops were recorded by
Lake-shore VSM.

4
H.M.Abd Elrhman
Fig. 6. Extraction efficiencies of Fe3O4, Nano-Cellulose, Cellulose citrate, Cellulose carbamate, Cellulose - acrylamide graft Fe3O4 @Nano-cellulose citrate, Fe3O4
@Nano-cellulose carbamate, and Fe3O4 @Nano-cellulose - acrylamide graft.
Fig. 7. Gamma rays spectrum of (a) initial concentration and (b) equilibrium concentration after adsorption process with conditions 0.2 g of Fe3O4 @nano-cellulose
citrate, 20 ml of ThCl4 (0.56%),T ¼ 301 K and pH ¼ 4.8.
2.4. Radioactivity measurements
High resolution gamma rays spectrometer of hyper pure germanium
detector (Ortec- Type: closed-end co-axial)) was used to measure the
activity of radioactive ions 228Ac, 212Pb, 212Bi and 208Tl in Bq/mL. Energy
calibration was done by 214Am, 137Cs, 57Co and 60Co gamma rays stan-
dards. Efficiency calibration by using 20 ml of mixed standards of 137Cs,
134
Cs, 75Co, 60Co and 65Zn.
2.5. Sorption experiments
Three aqueous solutions were prepared from 5 mL of (ThCl4-56%) in
5
Results in Materials 8 (2020) 100138
500 mL of distilled water. Then solutions at concentrations 0.56%, 0.28%
and 0.14% were prepared.
The batch adsorption experiment was conducted by mixed of 20 mL
of ThCl4 solutions (0.56%) with 0.2 g of each of the following adsorbents
for comparing their extraction capabilities;
Nano-cellulose, Cellulose citrate, Cellulose carbamate, Cellulose-
acrylamide graft, Fe3O4, Fe3O4@Nano-cellulose, Fe3O4@Nano-cellulose
citrate, Fe3O4@Nano-cellulose carbamate, and Fe3O4 @Nano-cellulose-
acrylamide graft at pH 4.8 for 1 h contact time in one average thickness
shell.
The extraction capabilities expressed as efficiency (E%) for each
adsorbent to adsorb 228Ac, 212Pb,212Bi and 208Tl were evaluated
H.M.Abd Elrhman Results in Materials 8 (2020) 100138

2θ (22.63 ) characterized the amorphous cellulose (Fig. 2a).

The average nano-crystalline size was calculated using Williamson-
Hall equation (3).

Kλ
βhkl cosθ ¼ þ 4εsinθ (3)
D

Where; βhkl is the line broadening at half the maximum intensity

(FWHM), θ is Bragg angle, K is the shape factor (equal 0.89 for
spherical crystal), the λ of Cukα radiation was 0.154 nm, D is the

Fig. 8. Effect of contact time on the adsorption of 228Ac,212Pb,212Bi and 208Tl at

conditions 0.2 g of Fe3O4 @Nano-cellulose citrate, 20 ml of ThCl4 (0.28%),T ¼
301 K and pH ¼ 4.8.

according to the following equation:

Ci  Ce
Eð%Þ ¼  100 (1)
Ci

where; Ci and Ce are initial and equilibrium concentrations of radio-

nuclides (Bq/mL).
The effects of contact time, initial concentration and pH on the
equilibrium adsorption capacity (qe) which was deduced in Bq/g by
using equation (2) were investigated.

qe ¼ ðCi Ce ÞV=W (2)

where; V (mL) is the volume of the ThCl4 solution and W (g) is the weight Fig. 9. Pseudo-first model.
of the dried adsorbent.

3. Results and discussion

3.1. Characterization

Fig. 1. shows TEM images of Fe3O4 and Fe3O4@nano-cellulose.The

magnetic nano-particles Fe3O4 composed of spherical shape with an
average diameter 8.6 nm as shown in (Fig. 1a) while Fe3O4 @nano-cel-
lulose showed in the dark colored Fe3O4 cores and gray colored cellulose
nano-particles with an average diameter 10.8 nm as shown in (Fig. 1b).
The XRD patterns of nano-cellulose, Fe3O4,Fe3O4@nano-cellulose,
Fe3O4 @nano-cellulose citrate, Fe3O4 @nano-cellulose carbamate and
Fe3O4@nano-cellulose-acrylamide graft were identified by the distance
d between the two plans of lattice in Å as shown in (Fig. 2).
The characteristic peaks of pure Fe3O4 nano-particles (Fig. 2b) at 2θ
are 30.06816̊, 35.46226̊, 43.14188̊, 53.48998̊, 57.10222̊ and 62.73194̊
are correspond to spinel structure of ferrite with a face-centered cubic
(fcc) structure.
The result indicates that the core shell was successfully formed
without damaging the spinel structure of Fe3O4 core during nano-
cellulose coating and surface functionalization. The broad band around Fig. 10. Pseudo-second-order model.

Table 4
Kinetic parameters of pseudo-first and pseudo-second-order models.
Parameters Pseudo-first-Order model Pseudo –Second-Order model

qe.exp (Bqg1) qe.cal (Bqg1) K1 (h1) R2 qe.cal (Bqg1) K2 (gBq1h1) R2

228
Ac 391 178.1 0.023 0.0 116 416.6 0.0288 0.9307
212
Pb 1429 563.6 0.098 0.5659 1428.5 0.0024 0.9896
212
Bi 817 304.9 0.079 0.1636 769.2 0.0084 0.9729
208
Tl 447.4 58.2 0.008 0.0017 454.5 0.0096 0.9881

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H.M.Abd Elrhman Results in Materials 8 (2020) 100138

cm1 CH rocking at 1322.67 cm1, non-symmetric alkoxy group C–O–C

at 1165.8 cm1, non-symmetric in phase ring 1114.57 cm1, skeletal
vibrations acyl group C–O at 1058.87 cm1, C–O at 1030.14 cm1, non-
symmetric out of phase ring (is characteristic of glucosidic ring in Ccell
structure) at 897.52 cm1, OH out of phase at 666.28 cm1 [17] as shown
in (Fig. 3a).
In Cellulose citrate pattern the -COOH group appeared at 1726.84
cm1,-C– – O of ester at 1655.35 cm1 (Fig. 3b). In Cellulose carbamate
carbonyl group C– – O at 1716.55 cm1, amide group at 1654.53 cm1
(Fig. 3c). In Cellulose- Acrylamide graft amide group at 1669.23 cm1 as
shown in (Fig. 3d).
(Fig. 4) shows the FT-IR patterns of Fe3O4, Fe3O4 @Nano-Cellulose,
Fe3O4 @Nano-cellulose citrate, Fe3O4 @Nano-cellulose carbamate and
Fe3O4 @Nano-cellulose - acrylamide graft.
Fe3O4 peak at 586.85 cm1 is attributed to Fe–O bond (Fig. 4a),
Fe3O4@Nano-Cellulose showed non-symmetric phase ring peak at
1116.66 cm1, skeletal vibrations acyl group C–O at 1065.68 cm1, and
non-symmetric out of phase ring at 810.67 cm1 that characterize cel-
lulose ring (Fig. 4b).
Fe3O4 @Nano-cellulose citrate displayed the peak of C–– O at 1625.62
Fig. 11. Langmiur model.
cm1 and -CH bending at 1376.97 cm1 (Fig. 4c). Fe3O4 @Nano-cellulose
carbamate and Fe3O4@Nano-cellulose- acrylamide graft give the peak of
-NH2 at 1631.21 cm1Fig. 4d and (Fig. 4e) respectively.
Table 5
Parameters of Langmiur model and Freundlich model. The magnetic hysteresis loops at room temperature were recorded for
Fe3O4, Fe3O4 @Nano-cellulose, Fe3O4 @Nano-cellulose citrate, Fe3O4
Model Langmiur model Freundlich model
@Nano-cellulose carbamate, and Fe3O4 @Nano-cellulose-acrylamide
qmax b R2 linKf n R2 graft as shown in (Fig. 5).
(Bq/g) (mLg1) (Bq1nmLng1)
The Saturation magnetization (Ms), Remanence (Mr) and Coercivity
228
Ac 114.9 0.12 0.9840 12.143 0.38 0.9918 (Hc) were measured. Fe3O4 gave the highest value of (Ms) in (amu/g)
212
Pb 1250 2 0.9985 7.576 4.84 0.9856 about all samples then it decreased due to the coating processes [7].
212
Bi 714.2 14 0.9938 6.686 8.21 0.9081
208
Tl 370.3 45 0.9982 5.947 16.50 0.8293
Fe3O4@Nano-cellulose citrate showed the lowest values of (Ms) in
(amu/g), (Mr) in (amu/g) and (Hc) in (G) indicating its small grain size
and less aggregation [18] suggesting enhancement in adsorption capa-
bility due to increasing the surface of adsorption as well the unique
chemical properties of citrate group. The magnetic parameters listed in
(Table 3) are characteristics of superparamagnetic behavior of the pre-
pared materials.

3.2. Optimization of sorption conditions

3.2.1. Extraction efficiencies of adsorbents

Fig. 12. Freundlich model.
crystalline size and ε is the strain induced in powders.
The grain sizes in (nm) and lattice strain are given in (Table 2) (the
average thickness shell can be calculated in all types from it).
FT-IR spectra of Nano-Cellulose, Cellulose citrate, Cellulose carba-
mate and Cellulose - acrylamide graft were investigated as shown in
(Fig. 3).
According to the Nano-cellulose pattern showed that stretch OH band
(O2-H——O6 intramolecular H-bond) at wave number 3047.94 cm1, CH
vibration of CH2 at 2902.80 cm1, water associated with nano-cellulose
at 1635 cm1, -CH2 bending at 1434.34 cm1, CH bending at 1373.88
The comparison between the capability of (Fe3O4, Nano-cellulose,
Cellulose citrate, Cellulose carbamate, Cellulose-acrylamide graft,
Fe3O4@Nano-cellulose, Fe3O4 @Nano-cellulose citrate, Fe3O4 @Nano-
cellulose carbamate and Fe3O4 @Nano-Cellulose-acrylamide graft) to
adsorb 228Ac,212Pb,212Bi and 208Tl were evaluated by calculating its
adsorption efficiency at conditions 20 mL of ThCl4 solutions(0.56%) and
0.2 g of adsorbent at pH ¼ 4.8, T ¼ 301 K and contact time 1 h and
displayed in (Fig. 6).
It clear that all adsorbents have variety of extraction efficiencies for
228
Ac, 212Pb, 212Bi and 208Tl. Fe3O4 Nano-particles showed high extrac-
tion efficiencies for both 208Tl, and 212Bi, intermediate value for 212Pb on
other hand 228Ac showed the lowest value, this may be attributed to the
magnetic nature of Fe3O4). The coating of Fe3O4 with nano-cellulose
(Fe3O4 @nano-cellulose) do not change significantly the extraction effi-
ciency values. The coating of Fe3O4 with modified nano-cellulose
enhanced the adsorption process for Fe3O4 @Nano-cellulose citrate and
Fe3O4 @nano-cellulose carbamate to remove both 208Tl, and212Bi. In
addition, a high percentage of 212Pb was adsorbed, as well as 228Ac
showed significant adsorption.
On other hand, Fe3O4 @nano-cellulose citrate and Cellulose citrate
showed the same rate of adsorption for 228Ac approximately, and this
indicates the role of citrate group to chelate with 228Ac.
The negative extraction efficiencies for 212Pb is due to the fast
decaying of 228Ac (6.1 h) to form 212Pb (10.6 h) in short period of time.
(Fig. 7a) shows the gamma rays spectrum of 228Ac,212Pb,212Bi and

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H.M.Abd Elrhman Results in Materials 8 (2020) 100138

Fig. 13. Effect of pH at conditions 0.2 g of Fe3O4 @nano-cellulose citrate, 20 mL of ThCl4 (0.28%),T ¼ 301 K.

Fig. 14. Effect of pH at conditions 0.2 g of Fe3O4 @nano-cellulose citrate, 20 mL

of ThCl4 (0.28%) and T ¼ 301 K.
208
Tl with 15 min counting time for 20 ml of ThCl4 with initial concen-
tration 0.56% and (Fig. 7b) shows equilibrium concentration after
adsorption process with Fe3O4 @Nano-Cellulose Citrate at conditions 0.2
g of Fe3O4 @Nano-Cellulose Citrate at T ¼ 301 K and pH ¼ 4.8.
Fig. 15. Effect of initial concentration on adsorption capacity at conditions 0.2
g of Fe3O4 @nano-cellulose citrate, 20mLof ThCl4, T ¼ 301 K and pH ¼ 4.8.
from the first order model equation (4) showed a wide difference be-
tween the predicted (qe-cal) and the experimental (qe-exp) with a low best
fitting (coefficient of determination) R2 values as shown in (Table 4).

lnðqe  qt Þ ¼ lnðqe Þ  K1 t (4)

3.2.2. Effect of contact time
The effect of contact time of adsorption process was investigated by
where; qe and qt are the adsorption capacity in (Bq/g) at equilibrium time
evaluating the equilibrium adsorption capacity (qe) of Fe3O4 @Nano-
and time t (h) respectively, and K1 is the kinetic rate constant of Pseudo-
cellulose citrate to adsorb of (228Ac,212Pb,212Bi and 208Tl) at contact time
first-order order.
from 1hr to 6hrs with conditions 0.2 g of Fe3O4 @Nano-cellulose citrate,
The values of qe and k1 were calculated from the plotting of lnðqe 
20 ml of ThCl4 (0.28%),T ¼ 301 K and pH ¼ 4.8. Fig. 8 shows that the
qt Þagainst t (Fig. 9).
rate of adsorption increased with an increase in the contact time till the
On other hand, the results obtained from the second order model (5)
0.5 hr in case 208Tl and 212Bi ions and 1 hr in case 228Ac and 212Pb then
showed a good agreement between the predicted (qe,cal) and experi-
slowed down until reaching the equilibrium between nanoparticles and
mental values (qe,exp) with high R2 value as shown in Table (4).
radiation ions due to the free surface of nanoparticles decreased with
time as a result of increasing the coverage by the bound ions. t 1 t
¼ þ (5)
qt K2 :q2e qe
3.2.3. Adsorption Kinetics
Pseudo-first-order and second order kinetic models were used to where; K2 is the kinetic rate constant. The best fitted relation between qt
t
interpret the adsorption mechanisms [19]. The results of (qe) obtained and t was used to calculate qe and K2, as shown in (Fig. 10) [21].

8
H.M.Abd Elrhman
3.2.4. Adsorption isotherms
The obtained experimental values of equilibrium adsorption capacity
(qe.exp) and the corresponding equilibrium concentrations (Ce) were
simulated with Langmuir isotherm model expressed in equation (6)
(commonly used to quantify the adsorption capacity at given tempera-
ture) to predict the maximum adsorption capacity qmax (the amount of
adsorbate at complete monolayer coverage) in Bq/g.
bqmax Ce
qe;exp ¼
1 þ bCe
where; qe given in (Bq/g) and Ce in (Bq/ml), b (ml/g) is a constant
related to the enthalpy of adsorption.
The plotting Cqe against Ce gives a linear relationship with a slope of
e The adsorbent capacity of adsorbent dependent on the type of adsorbent,
1 1
qmax and the intersection is bqmax as shown in (Fig. 11). The obtained re-
2 concentration of adsorbate. The magnetic behavior of sorbents acceler-
sults of qmax, b, and R are listed in (Table 5).
The obtained results from Langmuir model were compared with that
obtained from Freundlich model which is used in the case of multisite
adsorption isotherm for rough surfaces and this model expressed as:
qe ¼ Kf C1=n
e (7)
where: Kf is the Fruendlich constant related to the adsorption capacity
and nis a constant representing the degree of dependence of adsorption
on equilibrium concentration [20,21].
For estimating n, Kf and R2 the linear relation between lnqe and lnCe
was plotted to get the slope 1 n and the intersection ln Kf . As shown in
=
(Fig. 12). The values of n, Kf and R2 are listed in (Table 5).
The best fitting (coefficient of determination) R2 showed that the
adsorption of 212Bi and 208Tl on Fe3O4 @nano-cellulose citrate obeyed to
Langmiur model more than Freundlich model indicating the ions of these
nuclides form monolayer coverage on adsorbent. On other side, the
adsorption of 228Ac and 212Pb are related to Freundlich model and
Langmiur model with approximate degree indicating the dependence of
their adsorption on surface roughness, inhomogeneity, and adsorbate-
adsorbate interactions. These results confirm the nature of cleating pro-
cesses showed in (Fig. 6) for 212Bi and 208Tl ions occurred by OH group
and for 228Ac and 212Pb occurred by citrate group.
3.2.5. Effect of pH on adsorbent
The effect of pH on Fe3O4 @Nano-cellulose citrate was studied on
batches of Fe3O4 @nano-cellulose citrate (0.2g) in 20 ml distilled water
at different pH 2.09, 4.16, 6.63 and 11 by using NaOH(1N) and HCl(1N)
to adjust pH for 30 minutes then separated with a magnet. The adsorp-
tion experiment was carried out with conditions 0.2 g of Fe3O4 @nano-
cellulose citrate, 20 mL of ThCl4 (0.28%) and T ¼ 301K. The results
showed that, the pH ¼ 4.8 gave the best adsorption of 228Ac, 212Pb, 212Bi
and 208Tl as shown in (Fig. 13). This could be explained as the adsorption
capacity at low pH (strong acid medium) was low value may be due to the
abundance of hydronium ion (H3Oþ) which made increasing the
competition between it and radiation ions to adsorb on nanoparticles
surface, and with increasing the pH the adsorption capacity increased till
pH ¼ 4.8 then the adsorption capacity decreased with the pH may be the
effect the citrate group with hydrolysis at pH ¼ 7, after this value the
hydroxyl ion (OH-) increased which gave more negativity to nano-
particles, this leads to electrostatic attraction between these negatively
charged adsorption sites and positively charged of radiation ions,
increasing their adsorption (at pH ¼ 11) as shown in (Fig. 14) [22].
3.2.6. Effect of initial concentration
The adsorption of 228Ac,212Pb,212Bi and 208Tl ions on Fe3O4 @Nano-
cellulose citrate was investigated at different concentrations of ThCl4
0.56%, 0.28% and 0.14%(W/W%) at conditions 0.2 g of Fe3O4 @Nano-
cellulose citrate, 20 mL of ThCl4, T ¼ 301 K and pH ¼ 4.8. The results are
shown in (Fig. 15). It is clear that the increasing of initial concentration of
228
Ac, 212Pb, 212Bi and 208Tl ions enhance the adsorption capacity.
Results in Materials 8 (2020) 100138
This may be attributed to the high concentration of metal ions in-
creases the collisions between metal ions and adsorbent which enhanced
the adsorption process [10].
4. Conclusions
New sorbents based on superparamagnetic material of magnetite
nano-particles were synthesized and coated with nano-cellulose modified
nano-cellulose then applied to extract 228Ac, 212Pb, 212Bi and 208Tl ions
(6)
aqueous solutions.The result showed the adsorptions equilibrium were
reached at 0.5 hr in case 208Tl and 212Bi ions and 1 hr in case 228Ac and
212
Pb. The adsorption capacity for all adsorbents gave a high extraction
especially Fe3O4 @nano-cellulose citrate which added unique features.
crystal size, function group, pH of medium, contact time and initial
ated the separation of sorbents by using permanent magnet. Using
modified nano-cellulose as coating for Fe3O4 gives economic feasibility,
which is to be used in water treatment due to the low cost of production,
zero toxicity and suitability to apply to a large volume of solution.
Credit author statement
H.M.Abd Elrhman: Conceptualization, Methodology, Validation,
Formal analysis, Investigation, Resources, Data Curation, Writing,
Writing - Review & Editing, Visualization, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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