Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Thallium extraction in urine and water samples by
nanomagnetic 4-Aminothieno[2,3-d] pyrimidine-2-thiol
functionalized on graphene oxide
Seyed Jamilaldin Fatemi
a,*
, Mohammad Reza Akhgar
b
and Masoud Khaleghi Abbasabadi
c
a
Department of Chemistry, Shahid Bahonar University of Kerman, 133 -76169, Kerman, Iran
b
Department of Chemistry, Faculty of Science, Kerman Branch, Islamic Azad University, Kerman, Iran
C
Researcher in Nano Technology Center, Research Institute of Petroleum Industry (RIPI), P.O. Box 1998-14665, Tehran, Iran
ABSTRACT
Thallium is a water-soluble metal and extra dosage has toxicological
effect in human body. Thallium is readily absorbed by inhalation,
ingestion and skin contact. The symptomatology of thallium toxicity
was seen in patients with hemorrhage, bone/gastrointestinal problems,
delirium, convulsions and coma. So, accurate determination of
thallium in water and human urine is necessary. In this research,
a novel and applied method based on 25 mg of nanomagnetic
4-Aminothieno[2,3-d] pyrimidine-2-thiol functionalized on graphene
oxide (Fe
3
O
4
-ATPyHS@GO) was used for thallium extraction in 50
mL of water, wastewater and urine samples by dispersive magnetic
back-extraction of solid phase by 1 mL of nitric acid solution, the
spectrometry (F-AAS). The working/linear range, the limit of detection
(LOD), and preconcentration factor (PF) were achieved (4-1400
L
; 4-300 L
), 0.9 µg L
, and 50, respectively (Mean RSD%=1.8
water; 2.1 urine). The absorption capacity of GO and Fe
3
O
4
-ATPyHS@
GO adsorbent were achieved 7.2 mg g
-1
and 137.5 mg g
-1
for 5 mg
L
-1
of thallium, respectively. The procedure was validated by ICP-MS
analyzer.
Keywords:
Thallium,
Water and urine,
Nanomagnetic 4-Aminothieno[2,3-d]
pyrimidine-2-thiol functionalized on
graphene oxide,
Dispersive magnetic micro solid-phase
extraction
ARTICLE INFO:
Received 20 May 2021
Revised form 18 Jul 2021
Accepted 13 Aug 2021
Available online 28 Sep 2021
*Corresponding Author: Seyed Jamilaldin Fatemi
Email: fatemijam@uk.ac.ir
https://doi.org/10.24200/amecj.v4.i03.150
------------------------
1. Introduction
The Thallium use as in semiconductor and
optical industries. The concentration of
thallium in rocks and soil (limestone, granite)
ranges between 0.05-1.7 mg kg
and 1.7-55
mg kg
, respectively [1]. The organic slates
and carbon source have 1000 mg kg
thallium
[2], and high concentration of thallium exist
sulfur salts of thallium [3]. Contamination with
thallium is effected on the environmental and
human health. Thallium has toxic effect even at
sub ppb concentration and accumulate in plant,
vegetables, fruit, microorganisms, animals and
human tissues due to water soluble [4,5]. The
occupational exposure of thallium is 0.1 mg m
-2
for skin and more than 15 mg m
-2
is dangerous for
human. Thallium can be absorbed from inhalation,
ingestion and skin. So, the thallium toxicity must
be evaluated in patients through determination
in water, wastewater, urine, hair, nail and blood
samples. The toxicity of this element is higher
compared to mercury, cadmium and lead [6,7].
The mean daily diet contains 2 ng L
-1
thallium
69
Thallium extraction by Fe
3
O
4
et al
and the average content of thallium in the human
body was 0.1 mg. The concentrations in blood
and due to reference values
thallium has low concentration between 0.15–0.6
in serum
[8,9]. Groesslova and Wojtkowiak showed that
the toxicity of thallium is mainly related to the
similarity between Tl (I) ions and K ions, which
cause to the thallium interference with potassium
and disorder of potassiumassociated metabolic
processes. Also,
bonds and cysteine cross-linking and cause to
the keratin reduction [10,11]. The thallium-201,
a radioactive isotope, was used for evaluating
coronary artery disease. This type of thallium is
more than 4000 times less potent. Thallium-201
is useful in distinguishing toxoplasmosis from
Primary CNS lymphoma (PCNSL)in HIV
patients. Also, the thallium-201 scintigraphy
is useful to diagnose the Kaposi sarcoma, the
thyroid imaging and various tumors of the
lungs [12]. the acute thallium toxicity has been
reported between 6-15% in humans by health
organization and the dosage from 10 to 15 mg
kg
-1
is a lethal dose for humans. Elimination phase
for thallium stats about 24 hours’ post-exposure
and is mainly achieved through renal excretion
and the elimination phase may take up to 30 days
with long time. Symptoms of acute exposure
of thallium are gastrointestinal, CNC problem,
and skin [13,14]. The chronic exposure is
gastrointestinal symptoms include, the abdominal
pain, the vomiting and the diarrhea. Therefore,
due to adverse effect of thallium in human health,
the determination human urine, foods and waters
must be considered [15]. Based on the thallium
toxicity, the power technique must be used
for determining of thallium in environmental
(water) and human biological (urine) samples.
Numerous papers showed that the measurement
of this topic with different analytical methods
in various matrixes such as, the laser excited
[16], the anodic stripping voltammetry (ASV)
[17], the inductively coupled plasma optical
emission spectrometry (ICP-OES) [18]
atomic absorption spectrometry (FAAS) [19], the
electrothermal atomic absorption spectrometry
(ET- AAS) [19] and the high resolution inductively
coupled plasma mass spectrometry (HR-ICP-MS)
[20].
In this research, a novel method based on
nanomagnetic 4-Aminothieno[2,3-d] pyrimidine-
2-thiol functionalized on graphene oxide as a
Fe
3
O
4
-ATPyHS@GO adsorbent was used for the
extraction of thallium in the water, wastewater and
the urine samples. The thallium concentration was
determined based on dispersive magnetic micro
solid-phase extraction by F-AAS.
2. Experimental
2.1. Apparatus and Characterization
absorption spectrometer coupled (F-AAS, Varian,
USA). The Air-acetylene (C
2
H
2
) and the deuterium
lampas was adjusted The limit of detection (LOD)
and sensitivity of F-AAS obtained 0.2 mg L
-1
and
0.15 mg L
-1
. The HCL of Tl was adjusted based on
catalog book with wavelength of 276.8 nm, slit of
0.5 nm and current of 10 mA. All samples injected
to F-AAS by auto- injector (0.5-3 mL). The working
range and linear range of AT-AAS were obtained
0.2-75 mg L
and 0.2- 15 mg L
, respectively. The
electrothermal atomic absorption spectrophotometer
(ET-AAS, Varian, USA) was used for validation of
thallium in urine and water samples. For suppress of
ionization in F-AAS, the reagent of KNO
3
or KCl
was used as a 2000 mg L
-1
The
pH was calculated by digital pH meter (Metrohm
744, Swiss). The different buffer of the acetate (PH
3–6) were used for adjusting pH. The ultra-sonication
(Grant, U.K) and the Sigma 3K30 magnetic
centrifuge (30.000 rpm, UK) was used. The natural
from Merck chemical Company. The Perkin Elmer
Spectrum spectrophotometer (65 FT-IR, USA) was
used for FT-IR spectra. The PRO X-ray diffractometer
was used for
emission scanning electron microscope (FE-SEM)
were prepared by SEM of Tescan Mira-3.
70
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
2.2. Materials
All reagents with analytical grade such as; the
thallium solution (Tl NO
3
), the acids and base
solutions (HNO
3
, HCl, NaOH) were purchased
from sigma Aldrich (Germany). The standard
solution of thallium nitrate (CAS N: 10102-45-1,
Sigma, Germany) was prepared from stock of 1000
mg L
-1
solution in 1 % HNO
3
for further studies.
The standard solutions for calibration were daily
prepared by distilled water (DW) from Millipore
(USA). The other reagents such as acetone and
ethanol with analytical grade were purchased from
Merck (Germany). The citric acid was used for
phosphate citrate buffer for PH between 2.1–7.4
and the acetate buffer was used for pH from 2.8 to
6.2 which was purchased from Merck.
2.3. Synthesis of Fe
3
O
4
-ATPyHS@GO
Hummers method. 5 g of graphite powder was
mixed with 250 mL of H
2
SO
4
and stirred for 24
h. Then, 30 g of KMnO
4
was gradually added to
[21]. Due to
previous studies, 4-aminothieno[2,3-d] pyrimidine-
2-thiol (10 g) was added to 150 mL of ethanol and
DW (1:1 v/v). Then, 180 mg of GO was added to
the resulted solution at 35
o
C. The H
3
PO
2
(50 mL, 50
wt%) was added to product and stirred for 90 min.
The product of ATPyHS@GO was washed and
dried by DW and oven, respectively. The magnetic
nanostructure was prepared by co-precipitation
of FeCl
2
·4H
2
O and FeCl
3
·6H
2
O, in the presence
of 4-Aminothieno[2,3-d] pyrimidine-2-thiol graft
on GO (ATPyHS@GO). First, the mixture of
FeCl
2
·4H
2
O and FeCl
3
·6H
2
O was prepared with
a molar ratio of 1:2. For synthesis nanomagnetic
adsorbent, 10 mg of 4-aminothieno[2,3-d]
pyrimidine-2-thiol grafted on graphene oxide
(ATPyHS@GO) was solved to 10 mL of DW and
sonicated for 40 min. Then 125 mg of FeCl
2
·4H
2
O
and 200 mg of FeCl
3
·6H
2
O in 10 mL of deionized
water were added to remain solution at 25
C. For
adjusting of pH=11, the ammonia solution was
added at 65
C. After 20 min stirring, the product
was cooled at 25
C. Finally, the black Fe
3
O
4
-
ATPyHS@GO was centrifuged at 4000 rpm for 50
min, washed for 10 times (DW) and dried at 70
C
based on vacuum accessory [22-24].
Fig.1. Synthesis of nanomagnetic ATPyHS@GO adsorbent by 4-aminothieno[2,3-d]
pyrimidine-2-thioland and Fe
3
O
4
on GO [22-24]
71
Thallium extraction by Fe
3
O
4
et al
2.4. Extraction Procedure
and standard samples (4 - 300 µg L
) were used
for separation and determination of thallium ions
at pH 4-6. Firstly, 25 mg of Fe
3
O
4
-ATPyHS@
GO added to water, urine and thallium standard
solution and the sample sonicated for 3.0 min at
pH=5. After sonication, the Tl ions was chemically
absorbed on thiol groups (ATPyHS) of Fe
3
O
4
-
ATPyHS@GO adsorbent (Tl
+
……:SH-ATPy @
GO) and then, settled down in bottom of magnetic
centrifuge conical tube. Then, the thallium ions
were back-extracted from Fe
3
O
4
-ATPyHS@
GO at basic pH with NaOH solution (0.1 M, 0.5
mL) and was simply separated by the external
magnetic accessory. Finally, the remain solution
was determined by FAAS after dilution with DW
up to 1 mL (Fig.2). The procedure was round for a
blank solution without thallium ions for ten times.
The analytical parameters showed in Table 1. The
recovery of thallium extraction was calculated
by the equation 1. The C
i
and C
f
are the primary
determined by F-AAS (n=10).
Recovery (%) = (C
i
-C
f
)/C
i
×100 (Eq.1)
Table 1. The analytical parameters for determination thallium in water and urine samples based on Fe
3
O
4
-
Parameters Values
Working pH 4-6
Amount of Fe
3
O
4
-ATPyHS@GO adsorbent (mg) 25
Sample volume of water (mL) 50
Volume of sample injection 1.0 mL
Linear range for water
working range for water
Mean RSD %, n=10
4.0-300 L
-1
4.0-1400 L
-1
1.8
LOD for water 0.9 L
-1
Preconcentration factor 50
Volume and concentration of NaOH 0.5 mL, 0.4 M
Shaking time 3.0 min
R
2
= 0.9997
Fig.2. The extraction procedure of thallium in water and urine samples based
on Fe
3
O
4
-ATPyHS@GO adsorbent by
72
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
3. Results and Discussion
3.1. TEM Spectra
The TEM of Fe
3
O
4
-ATPyHS@GO and GO
adsorbent was prepared (Fig. 3a and 3b). Based on
the TEM images, both of GO and Fe
3
O
4
-ATPyHS@
GO have the thin sheets about 30-80 nm. The Fe
3
O
4
was seen as black point on surface of GO in TEM
of Fe
3
O
4
-ATPyHS@GO adsorbent (Fig. 3a).
3.2. FE-SEM Spectra
The morphology of Fe
3
O
4
-ATPyHS@GO and GO
electron microscopy (FE-SEM) (Fig. 4a and 4b).
Based on the SEM images, both of GO and Fe
3
O
4
-
ATPyHS@GO have the thin sheets nearly related to
each other. The SEM images of GO and Fe
3
O
4
@4-
PhMT-GO showed us, the HS and Fe
3
O
4
had no
effect on the morphology of the GO sheets. Also, the
nanoparticles of Fe
3
O
4
have a spherical morphology
on HS-GO with a diameter of 40 nm.
3.3. FTIR diagram
The infrared spectra of pure GO and Fe
3
O
4
-
ATPyHS@GO are presented in Figure 5.
The spectra of GO and Fe
3
O
4
-ATPyHS@GO
are showed to the stretching bands of (O-H;
Fig. 3a. TEM of the Fe
3
O
4
-ATPyHS@GO Fig. 3b. TEM of the GO adsorbent
Fig. 4a. FE-SEM of the Fe
3
O
4
-ATPyHS@GO
Fig. 4b. FE-SEM of the GO
73
Thallium extraction by Fe
3
O
4
et al
3415), (C=O; 1730), (C=C; 1624), and (C-O;
1061). Also, the peak of FTIR at range of 2600-
3500 cm
-1
belong to to the O-H and C=C(OH)
function. Moreover, the peak of 1400 cm
-1
and
2234 cm
-1
related to tertiary hydroxyl groups(OH)
and HS function on GO.
In –addition the peaks
at 628 cm
-1
and 583 cm
-1
belong to the Iron oxide
[22-24].
3.4. X-ray diffraction (XRD) patterns
The X-ray diffraction patterns of Fe
3
O
4
-ATPyHS@
GO was shown in Figure 6. GO have a single
O
2
groups. In both of GO and Fe
3
O
4
@4-PhMT-
GO adsorbent, the XRD peaks were observed at
o
which are belonged to (002)
and (100), respectively. Based on the XRD peak of
Fe
3
O
4
-ATPyHS@GO, the intensity of the peak at
HS and Fe
3
O
4
o
showed that the stability of O
2
functionalities even
after the functionalization of GO with HS or Fe
3
O
4
groups. The similar XRD peak of Fe
3
O
4
can be
seen for the Fe
3
O
4
-ATPyHS@GO adsorbent which
of Fe
3
O
4
. So, the functionalities of HS and Fe
3
O
4
were successfully done without changing in
structure of GO.
Fig. 5. The FTIR spectra of pure GO and Fe
3
O
4
-ATPyHS@GO adsorbents
Fig. 6. XRD patterns of (a) GO adsorbent and (b) Fe
3
O
4
-ATPyHS@GO adsorbent [22]
74
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
3.5. Optimizing extraction parameters
of thallium in water, wastewater and urine samples
was achieved by a novel Fe
3
O
4
-ATPyHS@
thallium
thallium based on Fe
3
O
4
-ATPyHS@GO adsorbent,
the extraction conditions must be optimized. So,
the effective parameters such as pH, the amount of
adsorbent, the eluent, the sample volume, and the
adsorption capacity must be studied.
3.5.1. pH effect
The pH of extraction of thallium in water and urine
samples must be evaluated and optimized. The favorite
pH cause to increase the adsorption of thallium ions
by the Fe
3
O
4
-ATPyHS@GO adsorbent. So, the
different pH between 2-11 was examined for thallium
extraction in water and urine samples by adjusting pH
with different buffer solutions. The results showed us,
the maximum extraction of the Fe
3
O
4
-ATPyHS@GO
adsorbent for Tl(I) was obtained at pH of 4-7. Also, the
recoveries for thallium were decreased at acidic pH
less than 4 and basic pH more than 7. So, the pH 5 was
selected as the optimal pH for extraction of thallium
in water and urine samples by the Fe
3
O
4
-ATPyHS@
GO adsorbent (Fig.7). The mechanism of extraction
of thallium was occurred by the dative bond of thiol
group [2(Ti
+
) ……..
2
:SH-ATPyHS@GO- Fe
3
O
4
) with
the positively charged of thallium(Tl
+
) at optimized
pH. In addition, the thallium ions participated
(Tl(OH)) at more than pH 7.5.
3.5.2. Amount of Fe
3
O
4
-ATPyHS@GO adsorbent
Foe high extraction of thallium in water/urine
samples, the amount of the Fe
3
O
4
-ATPyHS@
GO adsorbent evaluated at thallium concentration
. For this purpose, the various
amount of the Fe
3
O
4
-ATPyHS@GO adsorbent
between 5-50 mg were studied for Tl(I) extraction
method. As Figure 8, the best recovery for thallium
extraction was created by 20 mg of Fe
3
O
4
-ATPyHS@
GO adsorbent. So, 25 mg of the Fe
3
O
4
-ATPyHS@
GO adsorbent was used for further work.
3.5.3. Effect of eluents
The various eluents such as HNO
3
, H
2
SO
4
, NaOH
and CH
3
COOH were used for back extraction
thallium ions from the Fe
3
O
4
-ATPyHS@GO
adsorbent. In acidic and basic pH, the dative
bonding between the thiol group (HS) and thallium
(Tl) was started to dissociate (4>pH>6). So, after
break down the bonging, the thallium ions released
in eluent solution by elution. At pH more than 7, the
thallium participated as thallium hydroxyl (Tl-OH)
Fig.7. The effect of pH on thallium extraction in water and urine samples
by Fe
3
O
4
-ATPyHS@GO adsorbent
2 3 4 4.5 5 5.5 6 6.5 7 8 9
75
Thallium extraction by Fe
3
O
4
et al
and in low pH, the bonding of Tl-SH dissociated.
Due to results, the HNO
3
and NaOH has more
recovery as compared to H
2
SO
4
and CH
3
COOH.
The different acid solution with different volume
and concentration was used for back extraction Tl(I)
in water and urine samples (0.2-2.0 mol L
-1
, 0.1-0.5
the Tl ions were completely back-extracted from the
Fe
3
O
4
-ATPyHS@GO adsorbent by nitric acid and
NaOH solutions more than 1.0 mol L
-1
and 0.1 mol
L
-1
, respectively. Therefore, 0.1 mol L
-1
of NaOH
was used as an optimum eluent for this study. Also,
the effect of different volumes of eluents from 0.1
mL to 0.5 mL for thallium was checked. Therefore,
0.5 mL of NaOH (0.1 M) selected as optimum
elution (Fig. 9). Also, the more concentration of
NaOH (M>0.2) caused to the thallium participation
(Tl-OH).
0.1 0.2 0.3 0.5 1 1.5 2
Fig.9. The effect of eluent concentration on thallium extraction
in water and urine samples by the Fe
3
O
4
-ATPyHS@GO adsorbent
Fig.8. The effect of amount of Fe
3
O
4
-ATPyHS@GO adsorbent on thallium extraction in water
5 10 15 20 25 30 35 40 50
76
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
3.5.4.Effect of sample volume
water/urine samples is sample volume. The effect of
different volumes between 10-200 mL for Tl extraction
based on the Fe
3
O
4
-ATPyHS@GO adsorbent was
studied and optimized in water and urine samples (4-
). By results, the high recovery (%) was
occurred for 55 mL for urine and 70 mL for water
samples. So, 50 mL of sample volume was used for
(Fig. 10).
3.5.5. Effect of sonication time
The dispersion of Fe
3
O
4
-ATPyHS@GO adsorbent
increased the interaction between thiol group (HS) and
thallium ions at pH 5. By uniform dispersion of the Fe
3
O
4
-
ATPyHS@GO adsorbent, the chemical adsorption of
thallium occurred. Therefore, the extraction recovery
increased due to physical adsorption of GO and
chemical bonding of HS group in Fe
3
O
4
-ATPyHS@GO
adsorbent. Moreover, the sonication times was effected
on extraction rate. The various sonication times (1-10
minute) was used and the recoveries obtained. The
best recoveries were achieved at the sonication time of
2.5 min. Therefore, 3.0 min was used as the optimum
time for thallium extraction in water and urine samples.
After sonication, the magnetic adsorbent (Tl- Fe
3
O
4
-
ATPyHS@GO) was collected from the liquid samples
by extra magnet accessory.
3.5.6. The adsorption capacity
The Fe
3
O
4
-ATPyHS@GO adsorbent was dispersed in
water samples and the extractions of thallium ions from
liquid samples were followed many times and re-usage
of adsorbent calculated. The results showed, the Fe
3
O
4
-
ATPyHS@GO adsorbent can be used for 18 extraction
cycles at pH of 5.0. The absorption capacities (AC)
of the Fe
3
O
4
-ATPyHS@GO adsorbent depended on
the BET, the function group and size of adsorbent.
In batch system, 25 mg of the Fe
3
O
4
-ATPyHS@
GO
nanoparticles
was used in 50 mL of thallium
solution (5 mg L
-1
; ppm) at pH 5.0. After 10 minutes’
sonication, the AC of adsorbent calculated by F-AAS.
The adsorption capacities of the Fe
3
O
4
-ATPyHS@GO
adsorbent for Tl ions were obtained 137.5 mg g
-1
.
3.5.7. Interference of coexisting ions
The effect of main coexisting ions on thallium extraction
based on the Fe
3
O
4
-ATPyHS@GO adsorbent was
SPE procedure. So, the effect of various concentrations
of interfering ions (1-3 ppm) was studied for 50 mL
of water samples by proposed procedure at pH 5.0.
The main concomitant ions in water and urine were
selected and used for thallium extraction by the Fe
3
O
4
-
ATPyHS@GO adsorbent. The results showed that
the interference coexisting ions do not affect on the
thallium extraction in optimum conditions (Table 2).
Fig.10. The effect of sample volume on thallium extraction in water and urine samples
by the Fe
3
O
4
-ATPyHS@GO adsorbent
10 20 40 50 60 80 100 200
77
Thallium extraction by Fe
3
O
4
et al
3.5.8. Validation in real samples
and determination of thallium in water and urine
samples. The validation of results for the Fe
3
O
4
-
ATPyHS@GO adsorbent were shown in Table 3. For
validation, the real samples were spiked to different
concentration of standard solutions of thallium and
pH 5.0 (Table 3)
and high recovery for thallium ions were obtained
in water and human urine samples by nanoparticles
of the Fe
3
O
4
-ATPyHS@GO adsorbent. Moreover,
the standard reference materials were prepared in
water and urine samples with ICP-MS analyzer for
Fe
3
O
4
-ATPyHS@GO adsorbent (Table 4).
Table 3. Validation of methodology for thallium ions in water and urine samples based
on Fe
3
O
4
-ATPyHS@GO adsorbent by spiking of real samples
Sample* Added
(μg L
-1
)
*
Found (μg L
-1
) Recovery (%)
a
Well water
--- 56.4 ± 2.4 ---
50 104.6 ± 4.5 96.4
b
Wastewater
--- 146.6 ± ---
150 294.3 ± 13.4 98.5
Wastewater
c
--- 122.9 ± 5.9 ---
100 225.7 ± 11.2 102.8
Urine
--- 4.7 ± 0.2 ---
5 9.6 ± 0.5 98.0
Urine
--- 11.9 ± 0.4 ---
10 21.6 ± 0.9 97.0
--- 28.9± 1.3 ---
Urine 30 59.8± 2.7 103
a
Well water prepared from Varamin garden, Tehran,Iran
b
Wastewater prepared from chemical factory, Karaj, Iran
c
Wastewater prepared from petrochemical factory, Arak, Iran
Urine prepared from workers from car, chemical and paint factories, Iran
Table 2.
SPE procedure
Interferences ions
Mean ratio
(C
I
/C
Tl(I)
)
Mean ratio
(C
I
/C
Tl (I)
)
Recovery (%) Recovery (%)
Urine Water Urine Water
Mo
2+
, Ni
2+
, Co
2+
, Mn
2+
400 650 98.1 97.0
Zn
2+
, Cu
2+
700 900 96.5 98.3
Pb
2+
, Cd
2+
, V
3+
, Cr
3+
550 700 98.6 99.2
Br
-
, F
-
, Cl
-
, I
-
, NO
3
-
900 1200 97.9 98.5
Na
+
, K
+
, Ca
2+
, Mg
2+
1000 1300 97.3 98.8
Se
4+
350 400 97.1 97.6
Al
3+
, Be
+2
600 600 97.4 98.7
CO
3
2-
, PO
4
3-
, SO
4
2-
, NH
4
+
800 950 97.7 98.6
Hg
2
, Ag
+
200 300 96.8 97.4
Sn
2+
500 700 98.2 97.9
78
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
4. Conclusions
A simple and reliable method was used for
preconcentration, separation and determination
of Tl (I) in human urine and water samples by
was developed based on magnetic Fe
3
O
4
-
ATPyHS@GO adsorbent at pH 5.0 without any
organic chelating agent and organic solutions.
The proposed method based on the Fe
3
O
4
-
ATPyHS@GO adsorbent can be considered for Tl
reusability and fast separation phase. The newly
developed method was low interference, easy
usage for sample preparation in human urine
samples and also provides low LOD (0.9 µg L
),
RSD (1.8-2.1%) values as well as good PF (50)
and quantitative recoveries more than 95% for
thallium extraction in water and urine human
matrixes. So, the proposed method based on
magnetic nanoparticles and thiol groups on the
Fe
3
O
4
-ATPyHS@GO adsorbent can be considered
as a fast sample preparation technique with low
amount of adsorbent for thallium separation and
determination by F-AAS.
5. Acknowledgements
The authors wish to thank the Department of
Chemistry, Shahid Bahonar University of Kerman,
Kerman, Iran and Department of Chemistry of
Islamic Azad University, Kerman, Iran.
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Table 4. Validation of
Recovery (%)
Found
*
( μg L
-1
)
Added
ICP-MS ( μg L
-1
)
Sample
-----24.9 ± 1.2-----25.3 ± 0.5CRM1
97.044.3 ± 1.920.0
-----64.1 ± 2.8-----62.7 ± 0.7CRM 2
98.2113.2 ± 5.250.0
-----4.8 ± 0.2-----5.1± 0.2CRM 3
1029.9 ± 0.45.0
-----6.2 ± 0.3-----6.4 ± 0.2CRM 4
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