Anal. Method Environ. Chem. J. 3 (4) (2020) 5-16
Research Article, Issue 4
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Zinc based metal–organic framework for nickel adsorption
in water and wastewater samples by ultrasound assisted-
dispersive-micro solid phase extraction coupled to
electrothermal atomic absorption spectrometry
Negar Motakef Kazemi
a,*
a,*
Department of Medical Nanotechnology, Faculty of Advanced Sciences and Technology, Tehran Medical Sciences, Islamic
Azad University, Tehran, Iran
ABSTRACT
In this research, Zn
2
(BDC)
2
(DABCO) metal–organic framework
(MOF) as a solid phase was used for separation and preconcentration
toxic nickel ions (Ni) from water samples by ultrasound assisted-
dispersive-micro solid phase extraction coupled to electrothermal
atomic absorption spectrometry (USA-D-μ-SPE/ET-AAS).
The MOF nanostructure was characterized by eld emission-
scanning electron microscope (FE-SEM) and transmission electron
microscopey (TEM) for presentation of morphology and size of MOF
synthesis. By procedure, 25 mg of Zn
2
(BDC)
2
(DABCO) as MOF
adsorbent was added to 25 mL of water samples and then, Ni ions
chemically adsorbed based on dative bonding of nitrogen in DABCO
(1,4-diazabicyclo [2.2. 2]octane); N
2
(C
2
H
4
)
3
) at pH=8. The adsorbent
was separated from liquid phase by syringe cellulose acetate lters
(SCAF, 0.2 μm) and Ni ions back extracted from MOF adsorbent
before determined by ET-AAS. The maximum recovery of MOF for
nickel ions as a physically and chemically adsorption was obtained
34.6% and 98.8% at pH=3 and 8, respectively. The capacity adsorption
of Zn
2
(BDC)
2
(DABCO), MOF for nickel was acquired 125.7 mg g
-1
at pH=8. By procedure, the preconcentration factor (PF), LOD, and
linear range were achieved 48.7, 0.03 μg L
−1
and 0.10-2.88 μg L
−1
,
respectively (RSD<1.26). The validation of proposed method was
successfully obtained by ICP- MS analysis in real samples.
Keywords:
Metal–organic framework,
Nickel,
Adsorption,
Dispersive- micro solid phase
extraction,
Water sample,
Electrothermal atomic absorption
spectrometry
ARTICLE INFO:
Received 14 Sep 2020
Revised form 15 Nov 2020
Accepted 30 Nov 2020
Available online 29 Dec 2020
*Corresponding Author: Negar Motakef Kazemi
Email: motakef@iaups.ac.ir
https://doi.org/10.24200/amecj.v3.i04.123
------------------------
1. Introduction
The water pollution is one of the most important
issues in the world today [1-2]. The high
concentration of heavy metals in environment has
been attributed to population growth, economic
development and rapid industrialization in recent
years [3-5]. These toxic metals can enter to the
human body after release into the environment.
Exposure to heavy metals causes to poisoning,
mutagenicity, carcinogenicity and disease
in humans, as well as a serious threat to the
environment and public health [6]. Nickel is one
of the most toxic heavy metal for humans even in
6
Anal. Method Environ. Chem. J. 3 (4) (2020) 5-16
low concentrations. Nickel toxicity causes some
disorders in human body such as bone diseases,
damage to the liver and the kidney, bronchitis, lung
cancer and CNS problem [7, 8]. Nickel ions enter
into environment from waste water, water and
air from industries and factories such as battery
Company, mining and electroplating. Normal range
of nickel in human serum (0.2 µgL
-1
) is reported by
American conference of governmental industrial
hygienists (ACGIH). Also, the nickel values in
water samples are ranges from 3 to 10 µg L
-1
and
average levels in drinking water is between 2.0-
4.3 µg L
-1
[7,8]. Recently, the different techniques
include, ame atomic absorption spectrometry
(F-AAS) [9], electrothermal atomic absorption
spectrometry (ET-AAS) [10], ultraltration
[11], ion-exchange [12], chemical precipitation
[13], electrodialysis [14], adsorption [15],
spectrophotometry [16] and inductively coupled
plasma-mass spectrometry (ICP-MS) [17] were
used for nickel determination in water and human
biological samples. As difculty matrixes and trace
concentration in drinking waters and wastewater,
the sample preparation must be used to separation
Ni ions from samples. The different procedures
for sample preparation of Ni were reported in
water samples. For examples, the solid-phase
extraction (SPE), the functionalized magnetic SPE
[18], the dispersive liquid–liquid microextraction
method (DLLME) [19], ultrasound-assisted solid
phase extraction (USA-SPE) [20] and micro
SPE (D-μ-SPE)[21] were previously presented
for preparation of water samples by researchers.
Today, the nanotechnology has led to signicant
advances in different elds of science and
product innovation [22]. Nanomaterials have
been developed due to their special properties and
various application potentials [23, 24]. Recently,
the metal-organic frameworks (MOFs) have
expanded as porous hybrid organic–inorganic
materials [25, 26]. These materials synthesized
via self-assembly of primary building blocks
including metal ions (or metal clusters) as
metal centers, and bridging ligands as linkers
[27]. MOFs have been synthesized by different
methods such as solvothermal, hydrothermal,
ionic liquids, microwave, sonochemical, diffusion,
electrochemical, mechanochemical, and laser
ablation [28]. MOFs have received great attention
because of their unique properties in many areas
[28-29]. The ultrasound assisted-dispersive ionic
liquid-suspension solid phase micro extraction is
a good candidate method for Ni extraction from
waters [30].
In the present study, the nickel absorption is
one of the most considerable applications of
Zn
2
(BDC)
2
(DABCO) MOF in waters. So, The Zn-
MOF adsorbent based on USA-D-μ-SPE procedure
was used for nickel adsorption/extraction from
water samples and the concentration of nickel ions
determined by ET-AAS.
2. Experimental
2.1. Materials
All reagents with high purity and analytical
grade were purchased from Merck
(Darmstadt, Germany). Materials including
zinc acetate dihydrate (Zn(OAc)
2
.2H
2
O), 1,4
benzenedicarboxylic acid (BDC), 1,4-diazabicyclo
[2.2.2] octane (DABCO), dimethylformamide
(DMF) were purchased and used for synthesis
of Zn
2
(BDC)
2
(DABCO) MOF. The syringe
cellulose acetate lters (SCAF, 0.2 μm) purchased
from Sartorius, Australia (Minisart® Syringe
Filters). The GBC 932, electrothermal atomic
absorption spectrophotometer (ET-AAS, model
932, Australia) equipped with a graphite furnace
were used for the determination of nickel in water
samples. The samples were injected to graphite
tube with auto-sampler (20 µL). The ICP-MS
was used for determining of ultra-trace nickel in
water samples (Perkin Elmer, 1200 W; 2.0 L min
-
1
; 1-1.5 sec per mass; N2 gas). The pH meter with
the glassy electrode was used for measuring pH
in water samples (Metrohm, E-744, Switzerland).
The shacking of water and wastewater samples
were done by vortex mixer (Thermo, USA).
The standard solution of nickel nitrate (1%,
Ni(NO3)
2
was purchased from Sigma, Germany.
All of Ni standard 0.5-5 ppb was daily prepared
7
Nickel Extraction by Zn
2
(BDC)
2
(DABCO) MOF Negar Motakef-Kazemia
by dilution of the standard Ni solution with DW.
Ultrapure water was prepared from RIPI Co.
(IRAN). The pH was adjusted from 5.5 to 8.0 by
sodium phosphate buffer solution (0.2 M, Merck,
Germany).
2.2. Characterization
The MOF was characterized by scanning
electron microscope (FESEM) (SIGMA VP)
and transmission electron microscope TEM
(EM10C) microscopes from Zeiss Company.
X-ray diffraction (XRD) spectrum were prepared
by a Seifert TT 3000 diffractometer (Germany)
using wavelength 0.15 nm. The Fourier transform
infrared spectrophotometer (FTIR, IFS 88,
Bruker Optik GmbH, Germany) was used in the
200-4000 cm
−1
. Determination of nickel was
performed with ET-AAS.
2.3. Synthesis of MOF
The Zn
2
(BDC)
2
(DABCO) MOF was prepared
via the self-assembly of Zn
2+
ion as a connector,
DABCO as a bridging ligand, and BDC as
a chelating ligand. In a typical reaction, Zn
(OAc)
2
.2H
2
O (0.132 g, 2 mmol), BDC (0.1 g,
2 mmol), and DABCO (0.035 g, 1 mmol) were
added to 25 ml DMF [4]. The reactants were
sealed under reux and stirred at 90 °C for 15
min. Then, the reaction mixture was cooled to
room temperature, and ltered. The white crystals
were washed with DMF to remove any metal and
ligand remained, and dried in a vacuum. DMF
was removed from white crystals with a vacuum
furnace at 150 °C for 5 h.
2.4. General procedure of nickel adsorption
By proposed method, the Zn
2
(BDC)
2
(DABCO)
as metal–organic framework (MOF) was used for
extraction of toxic nickel ions (Ni
2+
) from water
samples by USA-D-μ-SPE procedure (Fig.1).
Firstly, 25 mg of Zn
2
(BDC)
2
(DABCO) adsorbent
added to 25 mL of water samples included
Ni standard solution and Ni ions chemically
adsorbed based on dative bonding of nitrogen
groups in DABCO material after shaking for 10
min at pH=8. Secondly, the Zn
2
(BDC)
2
(DABCO)
adsorbent separated from water samples by SCAF
(10 mL, 0.2 μm) and then the Ni loaded on the
MOF was back-extracted from solid-phase based
on changing pH by nitric acid solution (0.2 M,
0.25 mL). After dilution, the remained solution
was determined by ET-AAS after dilution with
DW up to 0.5 mL. Also, the adsorptions of the
Zn
2
(BDC)
2
(DABCO) adsorbent were evaluated
in different pH by USA-D-μ-SPE procedure and
capacities adsorption was obtained. The proposed
procedure was used for a blank solution without
any analyte (Ni) for 10 times. The calibration
curve for nickel in was prepared from LLOQ
to ULOQ ranges (0.1-2.88 µg L
−1
) and the PF
obtained by the curve-tting rule.
Fig. 1. Extraction procedure for nickel ions in water by Zn
2
(BDC)
2
(DABCO) adsorbent
8
Anal. Method Environ. Chem. J. 3 (4) (2020) 5-16
3. Results and Discussion
3.1. FE-SEM and TEM
Field emission scanning electron microscope (FE-
SEM) was used for evaluation of morphology of
MOF [Zn
2
(BDC)
2
(DABCO)] with an average
diameter of 100 nm (Fig. 2a). Transmission electron
microscope (TEM) was used for evaluation of
nanoparticles size and morphology of the MOF.
TEM showed the pore shape and size, the pore has
rod-shaped with many pore with different sizes
from 20-80 nm (Fig. 2b).
3.2. FTIR of Zn
2
(BDC)
2
(DABCO) MOF
The organic material and functional groups such
as NH, CO, SH in different adsorbents were
identied by FTIR analysis. The FTIR spectrum
of Zn
2
(BDC)
2
(DABCO) MOF was obtained after
calcination in KBr matrix (250 °C). As results, there
is no peak based on impurities and and it conrm
the completion of the synthesis. Also, various
peaks were presented such as 705 cm
−1
and 1000
cm
−1
for ZnO bonds, 3000 cm
−1
- 3500 cm
−1
for OH
of carboxylic acid, 1600 cm
−1
for CO stretching
Fig. 2a. FESEM of Zn
2
(BDC)
2
(DABCO) MOF Fig. 2b. TEM of Zn
2
(BDC)
2
(DABCO) MOF
Fig. 3. FTIR spectrum of the Zn
2
(BDC)
2
(DABCO) MOF.
9
Nickel Extraction by Zn
2
(BDC)
2
(DABCO) MOF Negar Motakef-Kazemia
bond and 1440 cm
−1
,1358 cm
−1
,1429 cm
−1
and
1550cm
−1
for aromatic compounds (Fig.3).
3.3. XRD of Zn
2
(BDC)
2
(DABCO) MOF
By application of XRD technique, the essential
information can obtain based on crystal structure
and product purity by XRD analysis. The XRD pat-
tern for the Zn
2
(BDC)
2
(DABCO) MOF was shown
in Figure 4. By results, all peaks are clear. In ad-
dition, the XRD pattern for the Zn
2
(BDC)
2
(DAB-
CO) has no peak belong to impurities. The crystal
structure of the Zn
2
(BDC)
2
(DABCO) conrm by
sharp peaks of XRD pattern. The size of the Zn
2
(B-
DC)
2
(DABCO) MOF was achieved about 45 nm by
Debye–Scherrer equation.
3.4. The pH optimization
The pH is the effective factor on adsorption
and extraction of nickel ions by USA-D-μ-SPE
procedure. So, the different pH between 2-10
was studied for extraction of Ni (II) in water
and wastewater samples. The experimental
results showed us, the Zn
2
(BDC)
2
(DABCO)
MOF was simply extracted Ni (II) ions from
water samples in a pH 7.5-8.5. Moreover, the
extraction efficiency was achieved about 98.7%
in pH of 8 but, the recoveries were reduced at
acidic pH less than 7 and basic pH more than
9.0. So, the optimum pH of 8 was used for
further works in this study. The extraction
mechanism of nickel ions in water samples
based on Zn
2
(BDC)
2
(DABCO) MOF take place
by the coordination of dative covalent bond of
N group as negative charge with the positively
charged Ni ions (Ni→:N) at pH=8. At lower pH
(pH< pH
PZC
), the surface of Zn
2
(BDC)
2
(DABCO)
MOF have positively charged and extraction
efficiency decreased as repulsion. Also, the
surface of Zn
2
(BDC)
2
(DABCO) MOF have
negatively charged at pH=8 and so the negative
charge between nitrogen group and Ni
2+
caused
to increased recovery. At pH more than 8, the
Ni ions started to participate (Ni(OH)
2
) and so,
the recovery decreased (Fig. 5). The best pH for
physical adsorption was achieved at pH between
3-4 with the mean recovery of 34.6%.
Fig.4. XRD pattern of the synthesized Zn
2
(BDC)
2
(DABCO) MOF
10
Anal. Method Environ. Chem. J. 3 (4) (2020) 5-16
3.5. The effect of sample volume
The inuence of sample volume for Ni extraction
based on Zn
2
(BDC)
2
(DABCO) MOF was studied
between 5-50 mL in water and wastewater samples
with LLOQ and ULLOQ ranges (0.1-2.88 µg L
-1
).
The results showed us the high recoveries were
achieved for 25 mL of water samples and wastewater
samples. So, 25 mL of sample was selected as
optimum volume for nickel extraction in water and
wastewater samples at pH=8. By increasing the
sample volume more than 25 mL, the extraction
recoveries were reduced between 43-52% (Fig. 6).
Fig. 5. The effect of pH on nickel extraction in water samples based on Zn
2
(BDC)
2
(DABCO)
MOF by USA-D-μ-SPE procedure
Fig. 6. The effect of sample volume on nickel extraction in water samples
based on Zn
2
(BDC)
2
(DABCO) MOF by USA-D-μ-SPE procedure
11
Nickel Extraction by Zn
2
(BDC)
2
(DABCO) MOF Negar Motakef-Kazemia
Fig. 7. The effect of MOF mass for nickel extraction in water samples
based on Zn
2
(BDC)
2
(DABCO) MOF by USA-D-μ-SPE procedure
3.6. The effect of Zn
2
(BDC)
2
(DABCO) MOF
For efcient recovery, the amount of
Zn
2
(BDC)
2
(DABCO) MOF must be evaluated
and optimized. Therefore, the amounts of
Zn
2
(BDC)
2
(DABCO) MOF between 5-50 mg
were examined for Ni(II) adsorption/extraction by
the USA-D-μ-SPE procedure. The results showed
that the quantitative recoveries in water samples
were obtained with 22 mg of Zn
2
(BDC)
2
(DABCO)
MOF for nickel extraction at pH=8. So, 25 mg of
Zn
2
(BDC)
2
(DABCO) MOF was used as optimum
of MOF mass for further process (Fig. 7). The
results showed us the extra dosage of MOF had no
effect on the extraction value in water samples.
3.7. The effect of eluent
The eluents with different volume and concentration
was used for back-extraction of nickel ions from
Zn
2
(BDC)
2
(DABCO) MOF. Acidic pH cause to
breakdown the dative bond between nitrogen group
in MOF and nickel ions (MOF-N: ….. Ni) and
then, the Ni (II) ions release into the eluent phase.
Therefore, a different volume of acid solution such
as HCl, HNO
3
, H
2
SO
4
and H
2
CO
3
with various
concentration was examined for back extraction
Ni(II) in water samples (0.1-1 mol L
-1
, 0.1-0.5
mL) by syringe cellulose acetate lters (SCAF, 0.2
μm). The results showed that 0.2 mol L
-1
HNO
3
as
elution phase
can efcient released the Ni (II) ions
from Zn
2
(BDC)
2
(DABCO) MOF to liquid phase.
So, 0.2 mol L
-1
of HNO
3
(0.1 mL) was selected as
the optimum concentration and volume of HNO
3
eluent in this study. As a result, the elution of solid
phase (Zn
2
(BDC)
2
(DABCO) MOF) with nitric acid
(0.2 M, 0.1 mL) was simply back extracted nickel
ions from MOF (Fig.8).
3.8. Validation
By USA-D-μ-SPE procedure, the nickel
extraction based on Zn
2
(BDC)
2
(DABCO) MOF
was obtained in water and wastewater samples.
The experimental results showed a validated data
for Ni (II) in tab water, drinking water, river water
and wastewater samples at pH=8 (Table 1). The
accuracy of the data were conrmed by spiking of
nickel standard solution to water samples based
on Zn
2
(BDC)
2
(DABCO) MOF adsorbent. Due to
results the efcient recovery for extraction Ni ions
in wastewater and water samples was achieved
by nanoparticles of Zn
2
(BDC)
2
(DABCO) MOF.
12
Anal. Method Environ. Chem. J. 3 (4) (2020) 5-16
The perfect extraction demonstrated that the
USA-D-μ-SPE technique had satisfactory results
for nickel in real samples at pH=8. In addition,
the standard reference materials (SRM) were
used for validating of DIL-S-μ-SPE procedure
(Table 2).
Fig. 8. The effect of eluents on nickel extraction based on Zn
2
(BDC)
2
(DABCO) MOF
Table 1. Validation of methodology for nickel extraction and determination in water
samples by spiking of samples by USA-D-μ-SPE procedure coupled to ET-AAS
Sample
Added
(μg L
-1
)
*
Found (μg L
-1
)
Recovery (%)
Tab Water
--- 0.454 ± 0.022 ---
0.5 0.948 ± 0.045 98.80
Drinking Water
--- 1.641 ± 0.072 ---
1.5 3.103 ± 0.147 97.46
a
Wastewater
--- 1.723 ± 0.084 ---
1.0 2.745 ± 0.133 102.22
Well water
--- 0.832 ± 0.042 ---
0.5 1.311 ± 0.058 95.81
River water
--- 1.074 ± 0.053 ---
1.0 2.108 ± 0.105 103.42
--- 1.824 ± 0.092 ---
b
Sea Water 1.0 2.787 ± 0.128 96.30
*Mean of three determinations of samples ± condence interval (P = 0.95, n =10)
a
wastewater dilution with DW (1:10)
b
Sea water dilution with DW (1:5)
13
Nickel Extraction by Zn
2
(BDC)
2
(DABCO) MOF Negar Motakef-Kazemia
3.9. Comparing with other methods
The USA-D-μ-SPE procedure was compared
to other published articles for extraction and
determination of Ni ions in water samples (Table
3). Due to table 3, the different methodology
and adsorbents compared for nickel extraction in
water samples. Many parameters such as LOD,
PF, RSD%, sample volume, capacity adsorption
and etc. compared together. The results showed
us, the USA-D-μ-SPE procedure was comparable
to other presented works in Table 3. Therefore,
the Zn
2
(BDC)
2
(DABCO) MOF with favorite
properties can be used for extraction of nickel in
water samples in optimized conditions.
Table 3. Comparing of USA-D-μ-SPE procedure with other published method
for nickel extraction in different matrixes
Methods Instrument Metal Matrix LOD(μg L
-1
) EF/PF %RSD Ref
SPE F-AAS Ni/Cu Water and biological
samples
0.6 200 3.1 [31]
IIPSPE UV-VIS NI Water 1.0 125 2.4 [32]
SPE F-AAS Ni, Ca,
Co, Cu
Tea, Water 1.0 10 2.0 [33]
ISSADSPE F-AAS Ni Water 0.7 50 2.5 [34]
NH-IS-SPE μS-FAAS Ni,Cr,Co Water and Food 2.74 205 3.5 [35]
SPE ICP-OES Ni Water 0.025 80 2.6 [36]
PPT-SPE F-AAS Ni Water 2.7 120 4.4 [37]
USA-D-μ-SPE ET-AAS Ni Water 0.03 48.7 1.26 This week
SPE: solid phase extraction
IIPSPE: Ion imprinted polymer- solid phase extraction
ISSADSPE: In-syringe solvent-assisted dispersive solid phase extraction
NH-IS-SPE: Needle hub in-syringe solid phase extraction
μS-FAAS: micro-sampling ame atomic absorption spectrometry
PPT-SPE: Pipette tip Solid phase extraction
Table 2. Determination of nickel in water samples based on Zn
2
(BDC)
2
(DABCO) MOF
by standard reference materials (SRM)
Sample Added (μg L
-1
) SRM Value (μg L
-1
) *Found (μg L
-1
) Recovery(%)
a
1643f ------- 1.5 1.49 ± 0.06 -------
1.5 ------- 2.91 ± 0.13 94.6
a
1643e ------- 1.5 1.59 ± 0.07 -------
1.5 ------- 3.15 ± 0.15 104.1
a
1640a ------- 0.6 0.63 ± 0.03 -------
0.5 ------- 1.12± 0.05 98.0
b
3136 ------- 1.0 1.02 ± 0.05 -------
1.0 ------- 1.98 ± 0.08 96.0
* Mean of three determinations of samples ± SD (P = 0.95, n =10)
a
Standard Reference Material 1643f (1.50), 1643e (1.50) and 1640a (0.6), trace elements in water, after dilution with DW (1:40)
b
NIST, SRM 3136, Sigma, after dilution with DW the concentration of 1.0 μg L
-1
daily prepared
14
Anal. Method Environ. Chem. J. 3 (4) (2020) 5-16
4. Conclusions
In this study, the Zn
2
(BDC)
2
(DABCO) MOF
adsorbent was synthesized by solvothermal method
at 90 °C via the self-assembly metal centers and
linkers using DMF solvent. Based on the results,
the MOF was propped as a good candidate for
nickel adsorption/extraction from water samples
by USA-D-μ-SPE procedure at pH=8. The syringe
cellulose acetate lters (SCAF, 0.2 μm) was used
for separation of Zn
2
(BDC)
2
(DABCO) MOF from
liquid phase and back-extraction of Ni ions from
adsorbent before determined by ET-AAS. The
Zn
2
(BDC)
2
(DABCO) MOF had the high recovery
between 94.6-104.1 for Ni extraction from water
samples. The proposed USA-D-μ-SPE method
had low LOD and RSD% with good reusability
about 21 times for water samples. Therefore, the
Zn
2
(BDC)
2
(DABCO) MOF caused to create the
efcient extraction of Ni ions in water samples based
on chemical adsorption. The nickel concentration
in remain solution has simply determined by ET-
AAS after back–extraction and dilution with DW.
5. Acknowledgement
The authors wish to thank from Department
of Medical Nanotechnology, Tehran Medical
Sciences, Islamic Azad University (IAUMS),
Iranian Research Institute of Petroleum Industry
(RIPI) and Iranian Petroleum Industry Health
Research Institute (IPIHRI) for supporting this
work.
6. References
[1] M.R. Mehmandoust, N. Motakef-Kazemi,
F. Ashouri, Nitrate adsorption from aqueous
solution by metal–organic framework MOF-
5, Iran. J. Sci. Technol. Trans. A-Sci., 43
(2019) 443–449.
[2] N. Kazemi, M. Yaqoubi, Synthesis of bismuth
oxide: removal of benzene from waters by
bismuth oxide nanostructures, Anal. methods
Environ. Chem. J., 2 (2019) 5-14.
[3] M. Odar, N. Kazemi, Nanohydroxyapatite
and its polycaprolactone nanocomposite
for lead sorbent from aqueous solution,
Nanomed. Res. J., 5 (2020) 143-151.
[4] N. Motakef-Kazemi, A novel sorbent based
on metal–organic framework for mercury
separation from human serum samples by
ultrasound assisted-ionic liquid-solid phase
microextraction. Anal. methods Environ.
Chem. J., 2 (2019) 67-78.
[5] E. Mosafayian Jahromy, N. Kazemi,
Speciation of selenium (IV, VI) in
urine and serum of thyroid patients by
ultrasound-assisted dispersive liquid-liquid
microextraction, Anal. methods Environ.
Chem. J., 3 (2020) 5-17.
[6] P.B. Tchounwou, C.G. Yedjou, A.K. Patlolla,
D.J. Sutton, Heavy metal toxicity and the
environment, Mol. Clin. Environ. Toxicol.,
101 (2012) 133-164.
[7] S.K. Seilkop, A.R. Oller, Respiratory cancer
risks associated with low-level nickel
exposure: An integrated assessment based
on animal, epidemiological, and mechanistic
data, Regul. Toxicol. Pharm., 37 (2003) 173–
190.
[8] Agency for Toxic Substances and Disease
Registry (ATSDR), Toxicological prole
for Nickel. Atlanta, GA: U.S. Department of
Health and Human Services, Public Health
Service, 2005.
[9] A.A. Satti, D.I. Temuge, S. Bektas, A.C. Sahin,
An application of coacervate-based extraction
for the separation and preconcentration of
cadmium, lead, and nickel ions prior to their
determination by ame atomic absorption
spectrometry in various water samples, Turk.
J. Chem., 40 (2016) 979–987.
[10] E.M. Sedykh, L.N. Bannykh, G.S. Korobeinik,
N.P. Starshinova, Determination of nickel
and vanadium in crude oils by electrothermal
atomic absorption spectrometry and
inductively coupled plasma atomic emission
spectroscopy after mineralization in an
15
Nickel Extraction by Zn
2
(BDC)
2
(DABCO) MOF Negar Motakef-Kazemia
autoclave, Inorg. Mater., 47 (2011) 1539–
1543.
[11] Q. Zhang, J. Gao, Y.R. Qiu, Removal
of Ni (II) and Cr (III) by complexation-
ultraltration using rotating disk membrane
and the selective separation by shear induced
dissociation, Chem. Eng. Process.,135 (2019)
236-244.
[12] A. Dabrowski, Z. Hubicki, P. Podkościelny, E.
Robens, Selective removal of the heavy metal
ions from waters and industrial wastewaters
by ion-exchange method, Chemosphere, 56
(2004) 91-106.
[13] M.M Matlock, B.S Howerton, D.A Atwood,
Chemical precipitation of heavy metals from
acid mine drainage, Water Res., 36 (2002)
4757-4764.
[14] T. Mohammadi, A. Moheb, M. Sadrzadeh, A.
Razmi, Modelling of metal ion removal from
wastewater by electrodialysis, Sep. Purif.
Technol., 41 (2005) 73-82.
[15] V. Srivastava, C.H. Weng, V.K. Singh, Y.C.
Sharma, Adsorption of nickel ions from
aqueous solutions by nano alumina: kinetic,
mass transfer, and equilibrium studies, J.
Chem. Eng. Data, 56 (2011) 4.
[16] R. Acharya, S. Kolay, A.V.R. Reddy,
Determination of nickel in nished product
alloys by instrumental neutron activation
analysis and spectrophotometry, J. Radioanal.
Nucl. Chem., 294 (2012) 309–313.
[17] D.P.C. De Quadros, D.L.G. Borges, Direct
analysis of alcoholic beverages for the
determination of cobalt, nickel and tellurium
by inductively coupled plasma mass
spectrometry following photochemical vapor
generation, Microchem. J., 116 (2014) 244–
248.
[18] S.Z. Mohammadi, H. Hamidian, L.
Karimzadeh, Z. Moeinadini, Simultaneous
extraction of trace amounts of cobalt, nickel
and copper ions using magnetic iron oxide
nanoparticles without chelating agent, J.
Anal. Chem., 68 (2013) 953–958.
[19] M. Nassiri, R. Gharanjik, H. Hashemi,
Spectrophotometric determination of copper
and nickel in marine brown Algae after
preconcentration with surfactant assisted
dispersive liquid-liquid microextraction,
Iran. J. Chem. Chem. Eng., 39 (2020) 117-
126.
[20] M. Behbahani, V. Zarezade, A. Veisi,
F. Omidi, S. Bagheri, Modication of
magnetized MCM-41 by pyridine groups
for ultrasonic-assisted dispersive micro-
solid-phase extraction of nickel ions, Int. J.
Environ. Sci. Technol., 16 (2019) 6431–6440.
[21] M. Rajabi, M. Abolhosseini, Magnetic
dispersive micro-solid phase extraction
merged with micro-sampling ame atomic
absorption spectrometry using (Zn-Al
LDH)-(PTh/DBSNa)-Fe
3
O
4
nanosorbent for
effective trace determination of nickel(II) and
cadmium(II) in food samples, Microchem. J.,
159 (2020) 105450.
[22] S. Hajiashra, N. M. Kazemi, Green synthesis
of zinc oxide nanoparticles using parsley
extract, Nanomed. Res. J., 3 (2018) 44-50.
[23] N. M. Kazemi, A.A. Salimi, Chitosan
nanoparticle for loading and release of
nitrogen, potassium, and phosphorus
nutrients, Iran. J. Sci. Technol. Trans A-Sci.,
43 (2019) 2781–2786.
[24] N. Motakef-Kazemi, M. Sandalnia, In situ
production and deposition of bismuth oxide
nanoparticles on cotton fabric, Iran. J. Sci.
Technol. Trans. A-Sci., 44 (2020) 1217–1223.
[25] S. Hajiashra, Preparation and evaluation of
ZnO nanoparticles by thermal decomposition
of MOF-5, Heliyon, 5 (2019) e02152.
16
Anal. Method Environ. Chem. J. 3 (4) (2020) 5-16
[26] B. Miri, S.A. Shojaosadati, A. Morsali,
Application of a nanoporous metal organic
framework based on iron carboxylate as drug
delivery system, Iran. J. Pharm. Res., 17
(2018) 1164-1171.
[27] N. Motakef-Kazemi, S.A. Shojaosadati,
A. Morsali, Evaluation of the effect of
nanoporous nanorods Zn
2
(bdc)
2
(dabco)
dimension on ibuprofen loading and release,
J. Iran. Chem. Soc., 13 (2016) 1205–1212.
[28] F. Ataei, D. Dorranian, N. Motakef-Kazemi,
Bismuth-based metal–organic framework
prepared by pulsed laser ablation method in
liquid, J. Theor. Appl. Phys., (2020). http://
doi: 10.1007/s40094-020-00397-y.
[29] N. Motakef-Kazemi, S.A. Shojaosadati, A.
Morsali, In situ synthesis of a drug-loaded
MOF at room temperature, Micropor.
Mesopor. Mat., 186 (2014) 73–79.
[30] H. Shirkhanloo, Z. Karamzadeh, J. Rakhtshah,
N. Motakef-Kazemi, A novel biostructure
sorbent based on CysSB/MetSB@MWCNTs
for separation of nickel and cobalt in
biological samples by ultrasound assisted-
dispersive ionic liquid-suspension solid
phase micro extraction, J. Pharm. Biomed.
Anal., 172 (2019) 285-294.
[31] M. Karimi, Sh. Dadfarnia, A.M. Haji
Shabani, Application of deep eutectic solvent
modied cotton as a sorbent for online solid-
phase extraction and determination of trace
amounts of copper and nickel in water and
biological samples, Biol. Trace Elem. Res.,
176 (2017) 207–215.
[32] H.R. Rajabi, S. Razmpour, Synthesis,
characterization and application of ion
imprinted polymeric nanobeads for
highly selective preconcentration and
spectrophotometric determination of Ni2+
ion in water samples, Spectrochim. Acta A,
153 (2016) 45–52.
[33] S.Z. Mohammadi, H. Hamidian, Tween 80
coated alumina: an alternative support for
solid phase extraction of copper, nickel,
cobalt and cadmium prior to ame atomic
absorption spectrometric determination, A. J.
Chem., 9 (2016) S1290–S1296.
[34] Jamshid Mod Nakhaeia, Mohammad
Reza Jamali, In-syringe solvent-assisted
dispersive solid phase extraction followed
by ame atomic absorption spectrometry for
determination of nickel in water and food
samples, Microchem. J., 144 (2019) 88–92.
[35] M. Shirania, F. Salaria, Needle hub in-
syringe solid phase extraction based a novel
functionalized biopolyamide for simultaneous
green separation/preconcentration and
determination of cobalt, nickel, and
chromium (III) in food and environmental
samples with micro sampling ame atomic
absorption spectrometry, Microchem. J. 152
(2020) 104340.
[36] M.S. Yalcın, S. Ozdemir, E. Kılınc,
Preconcentrations of Ni(II) and Co(II) by
using immobilized thermophilic geobacillus
stearothermophilus SO-20 before ICP-OES
determinations, Food Chem., 266 (2018)
126–132.
[37] M.A. Habila, Z.A. Alothman, E. Yilmaz, M.
Soylak, Activated carbon cloth lled pipette
tip for solid phase extraction of nickel(II),
lead(II), cadmium(II), copper(II) and cobalt(II)
as 1,3,4-thiadiazole-2,5-dithiol chelates for
ultra-trace detection by FAAS, Int. J. Environ.
Anal. Chem., 98 (2018) 171–181.
