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
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
2
(C
2
H
4
)
3
nickel ions as a physically and chemically adsorption was obtained
of Zn
2
(BDC)
2
(DABCO), MOF for nickel was acquired 125.7 mg g
-1
at pH=8.
,
Keywords:
Metal–organic framework,
Nickel,
Adsorption,
Dispersive- micro solid phase
extraction,
Water sample,
spectrometry
ARTICLE INFO:
Received 14 Sep 2020
Revised form 15 Nov 2020
Accepted 30 Nov 2020
Available online 29 Dec 2020
*Corresponding Author:
motakef@iaups.ac.ir
https://doi.org/10.24200/amecj.v3.i04.123
------------------------
1. Introduction
issues in the world today
concentration of heavy metals in environment has
been attributed to population growth, economic
years
human body after release into the environment.
mutagenicity, carcinogenicity and disease
in humans, as well as a serious threat to the
environment and public health . 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 . 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
. Recently, the different techniques
(F-AAS) , electrothermal atomic absorption
, ion-exchange , chemical precipitation
, electrodialysis , adsorption ,
spectrophotometry and inductively coupled
were
used for nickel determination in water and human
concentration in drinking waters and wastewater,
the sample preparation must be used to separation
for sample preparation of Ni were reported in
water samples. For examples, the solid-phase
, the dispersive liquid–liquid microextraction
, ultrasound-assisted solid
and micro
were previously presented
for preparation of water samples by researchers.
product innovation . Nanomaterials have
been developed due to their special properties and
various application potentials . Recently,
the metal-organic frameworks (MOFs) have
expanded as porous hybrid organic–inorganic
materials
via self-assembly of primary building blocks
including metal ions (or metal clusters) as
metal centers, and bridging ligands as linkers
methods such as solvothermal, hydrothermal,
ionic liquids, microwave, sonochemical, diffusion,
electrochemical, mechanochemical, and laser
ablation . MOFs have received great attention
because of their unique properties in many areas
liquid-suspension solid phase micro extraction is
a good candidate method for Ni extraction from
waters .
In the present study, the nickel absorption is
one of the most considerable applications of
Zn
2
(BDC)
2
was used for nickel adsorption/extraction from
water samples and the concentration of nickel ions
2. Experimental
2.1. Materials
All reagents with high purity and analytical
grade were purchased from Merck
(Darmstadt, Germany). Materials including
2
.2H
2
O), 1,4
(DMF) were purchased and used for synthesis
of Zn
2
(BDC)
2
from Sartorius, Australia (Minisart® Syringe
932, Australia) equipped with a graphite furnace
were used for the determination of nickel in water
was used for determining of ultra-trace nickel in
-
1
the glassy electrode was used for measuring pH
Ni(NO3)
2
was purchased from Sigma, Germany.
All of Ni standard 0.5-5 ppb was daily prepared
7
2
(BDC)
2
by dilution of the standard Ni solution with DW.
sodium phosphate buffer solution (0.2 M, Merck,
Germany).
2.2. Characterization
X-ray diffraction (XRD) spectrum were prepared
Bruker Optik GmbH, Germany) was used in the
200-4000 cm
. Determination of nickel was
2.3. Synthesis of MOF
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
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
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
(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
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
DW up to 0.5 mL. Also, the adsorptions of the
Zn
2
(BDC)
2
(DABCO) adsorbent were evaluated
procedure was used for a blank solution without
curve for nickel in was prepared from LLOQ
to ULOQ ranges (0.1-2.88 µg L
Fig. 1.
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
2
(BDC)
2
diameter of 100 nm (Fig. 2a)
from 20-80 nm (Fig. 2b).
3.2. FTIR of Zn
2
(BDC)
2
(DABCO) MOF
as NH, CO, SH in different adsorbents were
of Zn
2
(BDC)
2
(DABCO) MOF was obtained after
the completion of the synthesis. Also, various
peaks were presented such as 705 cm
and 1000
cm
for ZnO bonds, 3000 cm
- 3500 cm
for OH
of carboxylic acid, 1600 cm
for CO stretching
Fig. 2a.
2
(BDC)
2
(DABCO) MOF Fig. 2b.
2
(BDC)
2
(DABCO) MOF
Fig. 3.
2
(BDC)
2
(DABCO) MOF.
9
2
(BDC)
2
bond and 1440 cm
,1358 cm
,1429 cm
and
1550cm
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
-
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-
structure of the Zn
2
(BDC)
2
2
(B-
DC)
2
(DABCO) MOF was achieved about 45 nm by
Debye–Scherrer equation.
3.4. The pH optimization
procedure. So, the different pH between 2-10
was studied for extraction of Ni (II) in water
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
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
(pH< pH
), 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)
physical adsorption was achieved at pH between
3-4 with the mean recovery of 34.6%.
Fig.4.
2
(BDC)
2
(DABCO) MOF
10
Anal. Method Environ. Chem. J. 3 (4) (2020) 5-16
3.5. The effect of sample volume
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
).
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.
2
(BDC)
2
(DABCO)
Fig. 6.
based on Zn
2
(BDC)
2
11
2
(BDC)
2
Fig. 7.
based on Zn
2
(BDC)
2
3.6. The effect of Zn
2
(BDC)
2
(DABCO) MOF
Zn
2
(BDC)
2
(DABCO) MOF must be evaluated
Zn
2
(BDC)
2
(DABCO) MOF between 5-50 mg
were examined for Ni(II) adsorption/extraction by
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)
results showed us the extra dosage of MOF had no
effect on the extraction value in water samples.
3.7. The effect of eluent
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.
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
-1
HNO
3
as
elution phase
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
extraction based on Zn
2
(BDC)
2
(DABCO) MOF
was obtained in water and wastewater samples.
for Ni (II) in tab water, drinking water, river water
and wastewater samples at pH=8 (Table 1)
nickel standard solution to water samples based
on Zn
2
(BDC)
2
(DABCO) MOF adsorbent. Due to
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
for nickel in real samples at pH=8. In addition,
the standard reference materials (SRM) were
(Table 2).
Fig. 8.
2
(BDC)
2
(DABCO) MOF
Table 1.
Sample
Added
-1
)
*
-1
)
Recovery (%)
--- 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
a
wastewater dilution with DW (1:10)
b
Sea water dilution with DW (1:5)
13
2
(BDC)
2
3.9. Comparing with other methods
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,
the Zn
2
(BDC)
2
(DABCO) MOF with favorite
properties can be used for extraction of nickel in
Table 3.
for nickel extraction in different matrixes
Methods Instrument Metal Matrix LOD(μg L
-1
) EF/PF %RSD Ref
F-AAS Ni/Cu Water and biological
samples
0.6 200 3.1 31
NI Water 1.0 125 2.4 32
F-AAS Ni, Ca,
Co, Cu
1.0 10 2.0 33
F-AAS Ni Water 0.7 50 2.5 34
Ni,Cr,Co Water and Food 2.74 205 3.5 35
Ni Water 0.025 80 2.6 36
F-AAS Ni Water 2.7 120 4.4 37
Ni Water 0.03 48.7 1.26
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
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
-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
linkers using DMF solvent. Based on the results,
the MOF was propped as a good candidate for
nickel adsorption/extraction from water samples
for separation of Zn
2
(BDC)
2
(DABCO) MOF from
liquid phase and back-extraction of Ni ions from
Zn
2
(BDC)
2
(DABCO) MOF had the high recovery
between 94.6-104.1 for Ni extraction from water
had low LOD and RSD% with good reusability
Zn
2
(BDC)
2
(DABCO) MOF caused to create the
AAS after back–extraction and dilution with DW.
5. Acknowledgement
work.
6. References
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framework based on iron carboxylate as drug
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nanoporous nanorods Zn
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Anal. Method Environ. Chem. J. 3 (4) (2020) 17-29
Research Article, Issue 4
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
vitro separation and determination lead in blood serum of
micro solid phase extraction
Abhijit De
a, *
and S. Mojtaba Mostafavi
b
a
HITech institute of theoretical and computational chemistry, Shivakote, Hesaraghatta Hobli, Bengaluru, India
b
Department of Chemistry, Iranian-Australian Community of Science, Hobart, University of Tasmania, Australia
ABSTRACT
human body. So, the lead determination in blood/serum samples is very
3
H
10
N
4
O
2
S
2
plasma samples in battery
procedure, 25 mg of SM-NGO mixed with 10 mL of human blood/
serum or plasma samples and aspirated by 10 mL of syringe tube.
sulfur of SM-NGO adsorbent at pH=6 and the solid phase separated
L
-1
, 2.5 µg L
-1
samples.
Keywords:
Lead,
Human blood/serum,
Nano graphene oxide,
Dispersive-micro solid phase extraction
procedure
ARTICLE INFO:
Received 18 Aug 2020
Revised form 24 Oct 2020
Accepted 14 Nov 2020
Available online 29 Dec 2020
*Corresponding Author: Abhijit De
abhijit@iitcc.org, ade@actrec.gov.in
https://doi.org/10.24200/amecj.v3.i04.124
------------------------
1. Introduction
Heavy metals intakes to human body from air,
chromium (Cr
) and mercury (Hg) cause to serious
problem in humans and depended on way entrance
(Skin, lungs and gastrointestinal system) and
concentrations
gasoline, wastewater, x-ray protection and paint
are main source of lead in environment
battery factories are a main source of lead toxicity in
workers and cause to dysfunction in blood red cells,
and renal tissues . Also, the lead poisoning can
18
Anal. Method Environ. Chem. J. 3 (4) (2020) 17-29
be effected on human organs such as braine, renal,
liver and bone
body create by interaction of lead with proteins/
amino acids and cause anemia . On the other
hand the lead exposure causes to decrease the
erythrocytes cells (RBC) and reducing biosynthesis
health administration (OSHA) has reported that
-1
is
-1
.
Also, the food and drug administration (FDA) has
is below 250-300 µg L
-1
-3
by
NIOSH . Due to lead toxicity in human, the
accurate technology need to use for determination
of lead ions in the human blood/ serum samples.
Recently, the various methods were reported for lead
instrumental techniques such as the electrothermal
,
the inductively coupled plasma - atomic emission
, the high-performance liquid chromatographic
for lead determination in different matrixes.
Moreover, the sample preparation method is required
for extracting of lead ions in different biological
samples before determination by spectrometry
such as liquid-phase microextraction or dispersive
,
hydrophobic deep eutectic solvents based on
microextraction techniques, the headspace
solid-phase microextraction , the carrier-
, the
microextraction based on precipitation, the
, and
dispersive-micro solid phase extraction procedure
, were used for lead determination
in different human matrixes. Between them, D-µ-
sorbents are important factor for lead extraction
such as, the silica aerogel nanoadsorbent , the
magnetic phosphorus-containing polymer , the
magnetic metal organic frameworks MMOF,
the carboxylated graphene , the graphene
Oxide Sheets
with NiFe
2
O
4
were reported by chemistry and
showed that the different pretreatment techniques
based on metal nanoparticles, the drugs, the
extraction of heavy metals in human samples.
Recently, some drugs use for in-vitro and in-vivo
extraction of heavy metal in human samples and
antibiotic
SM can be complexed with metals in human body
and depended on pH and covalence bonding.
In this study, a new SM-NGO adsorbent
was used for determination lead in blood/serum
pretreatment.
2. Experimental
2.1. Instrumental
Lead in human blood and serum samples
put on burner and the fuel gas (air-acetylene), lamp
position, slit and light line were manually tuned.
Other parameters such as current and silt adjusted
19
Lead extraction by SM-NGO adsorbent Abhijit Dea et al
-1
).
and F-AAS in standard solutions was obtained
0.025 mg L
-1
and 0.07 mg L
-1
linear ranges of 0.08-6.0 mg L
-1
and 0.25-6.0 mg
L
-1
wavelength of 283.3 nm (5 mA). All samples were
injected with an auto-sampler injector from 100
-1
, 1.2 s/m, USA) as
+
+ e
), which are
Before mass separation, a beam of positive ions
has to be extracted from the plasma and focused
for determining of pH in liquid samples (Metrohm
100-500 rpm, ultrasonic heating (Iran) and Falcon
centrifuging (1000-4500rpm) prepared for this
study.
2.2. Reagents and Materials
-1
in 2 %
nitric acid) was purchased from Sigma (Germany).
All standard of lead (0.08, 0.1, 0.2, 0.5, 1, 2, 5
mg L
-1
) prepared by dilution of the stock lead
solution (1000 mg L
-1
Millipore, USA). Also, the sub-ppb concentration
(10-500 µg L
-1
) prepared by dilution of stock lead
standard solution (1 mg L
-1
100), nitric acid (HNO
3
), HCl, acetone, and ethanol
were purchased from Sigma Aldrich, Germany.
N-(5-methyl-1,3,4-
9
H
10
N
4
O
2
S
2
CASN:144-82-1) and the hydrophobic ionic
12
H
23
F
6
N
2
CASN: 304680-36-2) was purchased from Sigma
was prepared from chemistry department, India.
buffer solution (Na
2
4
/NaH
2
4
) from Merck
(Germany).
2.3. Sample preparations
All glasses such as vials, volumetric, dishes and
beakers cleaned with HNO
3
and H
2
SO
4
solution
(1:1, 2 M) for at least 12 h. After cleaning, all
250 µg L
-1
or >25µg dL
-1
and more than 500 µg
L
-1
is toxic. By procedure, 10 mL of the blood or
serum samples were prepared from 50 workers of
lead–acid batteries factories in India (Men, 20-55
samples prepared based on the world medical
association declaration of Helsinki for physicians
in human and all blood samples prepared from
worker with agreement forms.
2.4. Synthesis of GO@ Sulfamethizole
2.4.1.Preparation of GO
.
solution (H
2
SO
4
/ H
3
4
permanganate (KMnO
4
, 1.3 g) was slowly added
by stirring solution up to became black green.
2
O
2
slowly added to solution and stirred for
removal of excess of KMnO4. After cooling, the
hydrochloric acid (HCl:10 mL in 30 mL DW) was
of GO was washed with HCl and DW for 5 times
2.4.2.Synthesis of GO@Cl
Chlorinated graphene oxide was prepared due to
the Liu procedure . First, 1.0 g of GO, 20 ml
2
were added in a
20
Anal. Method Environ. Chem. J. 3 (4) (2020) 17-29
the excess of SOCl
2
was exit out from mixture by
distillation process based on vacuum condition.
nm). Finally, the product washed with acetone for 3
2.4.3.Synthesis of Sulfamethizole functionalized
on nanographene oxide (SM@NGO)
H
2
O with 5 mL of NaOH and then 1 mL of SM
solution were mixed in 60 mL ethanol (99%) by
an ultrasonic bath (25 min) in a 100 mL round
was added to mixture, and the mixture was
product was separated from the mixture by a
Membrane Filters (poly-
SM@NGO product washed with ethanol for many
2.5. Extraction Procedure
plasma samples were used for determination of lead
ions. Firstly, 25 mg of SM@NGO added to human
blood/serum and lead standard solution (10-500 µg
L
-1
) at pH=6.0 and aspirated by 10 mL of syringe
5.0 min, after shaking, the lead was extracted by
2+
2+
ions back-extracted from
acidic (0.5 mL, 0.5 M) and remain solution was
to 1 mL (Fig.1).
(10-500 µg L
-1
(0.1- 5 mg L
-1
Tga=m
1
/m
2
).
3. Results and discussion
3.1. Mechanism of Extraction by SM@NGO
H
2
O/NaOH solutions and then mixed with
the SM@NGO product was separated from the
membrane by washing and
on nanographene oxide caused to make favorite
adsorbent based on sulfur group (dative bond) for
lead extraction in blood, serum and plasma samples
Fig. 1.
21
Lead extraction by SM-NGO adsorbent Abhijit Dea et al
extraction with SM@NGO nanostructure caused
to increase the recovery up to 98.5 % as compared
the mechanism of lead extraction in serum, blood
and plasma samples depended on sulfur group
(Fig.2).
3.2. SEM, TEM and FTIR of SM@NGO
and used
30-100 nm which were shown in Figures 3 and 4,
Fig.2.
Fig.3. Fig.4.
22
Anal. Method Environ. Chem. J. 3 (4) (2020) 17-29
and SM@NGO adsorbent was shown in Figure 5.
is about twice as strong as a C-N single bond,
these groups vary in the same order, ranging from
1100 cm
-1
for C-N, to 1660 cm
-1
for C=N. Also,
symmetric and a symmetric traction for sulfur bond
(S-C) ranging from 1135-1165 cm
-1
and1310-1360
cm
-1
-1
,
S-H bond in 2570 cm
-1
, C-H bond in 3000 cm
-1
and
N-H bond in 3400 cm
-1
observed.
NGO were shown in Figure 6. XRD of graphene
Fig.6.
Fig.5.
23
Lead extraction by SM-NGO adsorbent Abhijit Dea et al
related to the oxygen groups which are intercalated
42.60
o
are related to the diffraction planes of (002)
and (100) respectively, which can be showed in both
of the XRD of GO and SM@NGO.
3.3. Optimization of extraction parameters
NGO adsorbent was used for the extraction and
parameters such as pH, sample volume and amount
3.3.1.Inuence of pH
battery workers was depended to pH. So, the pH of
can be affected on increasing /decreasing extraction
solutions help us to improved extraction recovery by
between 2-10 was evaluated by lead concentration
from 10 to 500 µg L
-1
high extraction of lead ions in human biological
samples was obtained at pH of 6.0 by SM@NGO
adsorbent. On the other hand, the recoveries can be
decreased at acidic or basic pH. So, the pH point of
(Fig.7).
Based on extraction mechanism, the coordination
of dative bond of sulfur as negative charge in SM@
2+
were
5.5), the SM@NGO adsorbent protonated and
surface of adsorbent got the positively charged. Due
to the electrostatic repulsion, the recoveries of lead
pH(6), the surface of SM@NGO have negatively
2+
ions
3.3.2.Inuence of SM@NGO amount
extraction in human samples has studied with lead
concentration between 10-500 µg L
-1
as a low and
high LOQ ranges. For this proposed, 1-50 mg of
SM@NGO adsorbent were used for lead extraction
in serum, blood, plasma and standard solutions
showed that the maximum of lead extraction in
human samples was achieved for 22 mg of SM@
NGO nanostructure. So, 25 mg of SM@NGO
adsorbent was used for further work (Fig. 8)
extra mass of 25 mg had no effect on recovery of
lead extraction in human samples.
Fig.7.
24
Anal. Method Environ. Chem. J. 3 (4) (2020) 17-29
3.3.3.Inuence of sample volume
Sample volume is an effective parameter for
extraction lead ions in human biological samples
such as serum, blood and plasma. So, the lead
extraction for sample volume between 1-30 mL was
concentration ranges (10-500 µg L
-1
) by the SF-D-
(Fig. 9)
10 mL was selected as optimum volume of human
samples for lead extraction with 25 mg of SM@NGO
Fig.8.
Fig.9.
25
Lead extraction by SM-NGO adsorbent Abhijit Dea et al
3.3.4.Inuence of volume and concentration of
eluents
of eluents such as HCl, HNO
3
, NaOH and
CH
3
COOH for back-extraction of lead ions from
used for back-extraction lead from adsorbent by
different volume of eluents between 0.5-2 mL
(0.2-1 M). After pushing the plunger of syringe,
membrane was performed by different eluents.
due to participate of lead hydroxyl in basic pH,
solution can be used for back-extraction of lead
the lead ions were simply back-extracted from
SM@NGO adsorbent by nitric acid solution more
than 0.4 mol L
-1
-1
of nitric
acid (HNO
3
) was used as optimum concentration
SM@NGO by 0.5 mL of HNO
3
. Finally, the
lead concentration in remained solution was
DW up to 1 mL.
3.3.5.Membrane lter reusing
by several extraction and elution cycles under
extraction processes and then rinsed by 5 mL
decrease in extraction recoveries of lead ions.
was hardly done and so, the extraction recovery
decreased more than 18 adsorption–elution
cycles.
3.3.6.Adsorption capacity
extraction with the SM@NGO packed Millex-
capacity. So, the adsorption capacity of 25 mg
human sample containing 5 mg L
investigated at pH 6 in static system. After adjusting
pH with favorite buffer solution, the mixture was
the residual concentrations of lead in the Millex-
57.5 mg g
and 162.1 mg g
, respectively.
3.3.7.inuence of Interference ions
extraction in human samples was examined by
the effect of different interference ions on lead
extraction, the various ions (0.5-2 mg L
-1
) added to
-1
at pH 6.0. So,
the most of the concomitant ions in human blood
such as Cu, Zn, Mn, Mg, Se, Li, F, NO
3
, HCO
3
,
Ca, Na an K were considered for lead extraction
showed, the interference coexisting ions had no
effect on lead extraction by proposed method.
(Table1)
biological samples in the present of the interference
coexisting ions.
3.3.8.Determination of lead in real samples
and determination of lead ions in human samples
the results, the human blood, serum and plasma
samples were spiked with lead standard solution
based on SM@NGO nanostructure before
of spiked samples demonstrated that the SM@
NGO adsorbent had satisfactory results for lead
26
Anal. Method Environ. Chem. J. 3 (4) (2020) 17-29
extraction and determination in human samples
at pH=6.0 (Table 2). Also, 10 mL of the blood or
serum samples were prepared from 50
workers of lead–acid batteries factories in India
and compared to healthy peoples (Table 3).
for validating of methodology based on SM@NGO
by the proposed procedure (Table 4)
Table 1.
Interfering Ions
Mean ratio
(C
I
/C
Pb(II)
)
Recovery (%)
Pb(II) Pb(II)
Cr
3+
, Se
2+
, Mn
2+
, 600 97.4
Zn
2+
, Cu
2+
700 98.6
I
-
, Br
-
, F
-
, Cl
-
1200 97.2
Na
+
, K
+
, Li
+
1000 99.2
Ca
2+
, Mg
2+
800 97.7
Ni
2+
, Co
2+
450 98.4
CO
3
2-
4
3-
, HCO3
-,
NO
3
-
950 96.6
Table 2. Determination of lead based on SM@NGO adsorbent and spiking samples
*Sample
Added
(μg L
-1
)
*
Found (μg L
-1
)
Extraction efciency (%)
Blood
--- 9.7 ± 224.2 ---
200 17.8 ± 418.6 97.2
--- 2.8 ± 55.4 ---
50 4.8 ± 106.7 102.6
Serum
--- 7.6 ± 168.9 ---
150 14.3 ± 311.6 95.1
Blood
--- 8.2 ± 178.8 ---
150 13.8 ± 322.3 95.6
Serum
--- 9.4 ± 192.3 ---
200 19.3 ± 399.5 103.6
--- 4.2 ± 88.5 ---
100 8.4 ± 186.8 98.3
27
Lead extraction by SM-NGO adsorbent Abhijit Dea et al
Table 3.
-1
)
*
Sample
b
Workers (n=50)
b
Healthy peoples (n=50)
a
Workers
Intra-day Inter day Intra-day Inter day r P value
Blood 352.8 ± 15.7 360.2 ± 16.2 33.1 ± 1.4 29.5 ± 1.3 0.092 <0.001
Serum 276.7 ± 12.6 281.2 ± 13.9 24.6 ± 1.1 28.2 ± 1.2 0.112 <0.001
147.5 ± 6.8 152.4 ± 7.3 12.8 ± 0.6 14.6 ± 0.7
0.086 <0.001
a
b
*
50 workers of lead–acid batteries factories in India (Men, 20-55 age)
Table 4.
Recovery (%)Found
*
( μg L
-1
)AddedCRM*( μg L
-1
)Sample
-----135.8 ± 6.5-----139.5 ± 0.8Caprine blood, level 2
97.8233.6± 11.4100
-----272.6 ± 13.1-----277.6 ± 1.6Caprine blood, level 3
96.5465.7± 21.8200
-----84.2 ± 4.4-----86.4 ± 2.1
94.6131.5 ± 4.450
*
-1
-1
4. Conclusions
A novel SM@NGO adsorbent was used for lead
separation/extraction in human blood, serum and
separating solid phased from liquid phase. By
low cost, the fast separation and simple method
trace amount of SM@NGO as a solid-phase caused
to extract the lead ions from the human biological
for lead separation/extraction/preconcentration in
human blood samples with low interference ions,
good reusability and simple sample preparation
nanostructure was used as a perfect adsorbent for
determination and extraction of lead in blood,
5. Acknowledgments
computational chemistry, India
28
Anal. Method Environ. Chem. J. 3 (4) (2020) 17-29
6. References
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amount of lead in water samples, Bull. Chem.
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Anal. Method Environ. Chem. J. 3 (4) (2020) 30-39
Research Article, Issue 4
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Adsorption methodology: Synthesis of Nano-
structured nitrogen-doped porous carbon adsorbents for
perchloroethylene vapor adsorption
Mohammad Ghasemi Kahangi
a,b
, Alimorad Rashidi
b*
and Mohammad Samipoorgiri
a
a
Chemical Engineering Department, Islamic Azad University, North Tehran Branch, Tehran, Iran
b
Carbon and Nanotechnology Research Center, Research Institute of Petroleum Industry, Tehran, Iran
ABSTRACT
be easily transported and remain in the atmosphere due to its volatility
and stability properties. As a result, there is a crucial need to reduce
this pollution to the extent permitted by international standards.
Gas chromatography–
mass spectrometry
(ACs) doped with nitrogen functional groups were prepared using
the walnut shell as a precursor to evaluate their adsorption capacity
2
adsorption-desorption, and the Fourier
the physical-chemical properties of the ACs. It is found that the
(KNCWS) due to their structural and surface charge properties. By
with experimental data that could indicate reversible adsorption of
mg/g for KNCWS-11, KNCWS-21, and KNCWS-31, respectively.
Keywords:
Adsorption procedure,
Gas chromatography mass spectrometry,
Nitrogen-doped adsorbent.
ARTICLE INFO:
Received 12 Aug 2020
Revised form 5 Oct 2020
Accepted 12 Nov 2020
Available online 30 Dec 2020
* Corresponding Author: A.M. Rashidi
rashidiam@ripi.ir
https://doi.org/10.24200/amecj.v3.i04.125
------------------------
1. Introduction
Atmospheric air, as an important topic of the
only contains natural and vital compounds, but also
a set of undesirable and unnatural materials .
Since the existence of volatile organic compounds
and many efforts have been made to removal
them in recent years . In addition, numerous
31
matter . According to various sources, volatile
organic compounds in atmospheric air are divided
into several main groups of alkanes, alkenes,
alkynes, aromatics, volatile organic compounds
of chlorine, and volatile organic compounds of
sulfur. Chlorine volatile organic compounds are
much more environmentally toxic than other
known as stable, biogenic, and biodegradable
compounds in the environment. Most of them are
to research effective techniques for managing
economically viable
tetrachloroethylene) as a representative of chlorine
ethylenes is a synthetic chlorine hydrocarbon known
as a solvent in industrial processes like metal
degreasing, drying, and drug, pesticides, adhesives,
. Due to the prevalence
of leakage and its inappropriate disposal, large
the environment in industrial
sites
the ambient atmosphere . According to OSHA,
effects that can damage to the central nervous
system in humans . Many methods have been
reported to control environmental pollution, such
as adsorption, advanced oxidation, electrochemical
and photocatalytic method. Because of low cost,
simplicity in design, and operation, the adsorption
method is widely used among the various methods
to remove the Cl
still a challenge and need more attention in this
regard. Zeng et al. (2015) found that activated
of 8 g/L and an initial concentration of 100 mg/L
can reach 97.83%. Adsorption kinetics indicates
monolayer, and multilayer adsorption process
joint with a physical process that occurs through
an ion-exchange surface adsorption mechanism
. In the adsorption process, the price of the
adsorbent is one of the most important factors in
the economics of the process, so most researchers
try to build and select a cheap adsorbent in this
process . Lignocellulose wastes are a good
option for cheap adsorbents, as the existing wastes
and economically competitive with other methods.
In addition, the solid phase extraction as analytical
techniques, such as the needle trap extraction,
the tube extraction, the sorption trap, solid-phase
waste production and greenhouse gas emissions.
Accordingly, In this research, by using the walnut
carbons were activated by KOH and the effect of in
situ N-doping on the textural properties as well as
addition the proposed procedure based on nitrogen-
2. Experimental
2.1. Apparatus and Reagents
injector was used for etrachloroethylene analysis
in air (Agilent GC, 7890A, GC-MS, Netherland).
in Agilent GC. Due to injection process, the slide
of plunger carrier down and tighten the plunger
32
Anal. Method Environ. Chem. J. 3 (4) (2020) 30-39
valves introduce a sample into the carrier gas
stream and valves were used to inject a sample gas
in gas streams. Iranian walnut shell was used as the
precursor of nanocarbons. Moreover, KOH, urea,
and HCl with analytical grade were purchased from
2
CH
2
N(CH
2
62-9). Acetone and ethanol prepared from Sigma,
Germany.
2.2. Preparation of N-doped nanocarbons
Walnut shell was respectively crushed, washed,
as a source of nitrogen–was mixed with different
doped carbon was mixed with KOH with the ratio
of 1:4 and activated under N
2
using a heating rate
of 7.5
o
as-prepared samples were washed with 1 M HCl
as-prepared samples were denoted as KNCWS-xy
in which xy represents the ratio of urea to CWS.
2.3. Characterization
diameter, and total pore volume, adsorption/
desorption isotherm of nitrogen was performed
provide the morphology of as-prepared ACs, a
collected from the absorbance intensities of
-1
wave number range.
2.4. Procedure
Figure 1
laboratory system operating according to the law of
thermodynamic equilibrium between the liquid and
pressure.
Continuous N
2
2
changing the ratio of concentrated and dilute N
2
2
sample located in the adsorbent bed. Contaminated
N
2
passed through the adsorbent and the process
Fig. 1.
33
the refractive index, the time required for saturation
can be achieved
3. Results and Discussion
3.1. FE-SEM
shell (Fig. 2a) has a smooth, pore-free surface in
which, after nitrogen doping (Fig. 2b), a number
of macropores are seen on the sample. Figure 2c
shows a spongy structure containing uniform,
that severe morphological changes have occurred
during the activation process and that the active
by physical adsorption of N
2
.
3.2. Physical Properties
N
2
adsorption/desorption isotherms were measured
to evaluate the textural properties of the samples.
Figure 3a are of type
desorption is of type H4. According to research,
H4 type hysteresis rings are related to the narrow
slit of the specimen
curvature in the relative pressure between 0 and
0.4 owing to the presence of cavities larger than
the average adsorbed diameter. On the other hand,
Fig. 2.
34
Anal. Method Environ. Chem. J. 3 (4) (2020) 30-39
more curvature of the isotherm knee at low relative
pressure and a slight increase in N
2
adsorbed
with increasing pressure indicate expansion
hysteresis ring exhibited at a relative pressure of
0
> 0.4) . As can
be seen from the wider circle of KNCWS-21
and KNCWS-11 hysteresis, the participation
width of 2.48 nm for KNCWS-21 and 2.41 nm for
KNCWS-33 . Based on the distribution shown
in Figure 3b,
less than 10 nm, which indicates the presence of
both micropores and mesopores. With increasing
the urea to carbon ratio from 1:1 to 2:1, the peak
intensity in the pore distribution curves of the
samples increased and then decreased to a ratio of
the KNCWS-31 sample compared to KNCWS-21
and occurred due to the destruction of the walls
between the cavities or the blockage of the cavities
with excessive nitrogen (.
Fig. 3. N
2
(a)
(b)
35
3.3. FT-IR
Figure 4
tests (a) CWS, (b) NCWS-21, and (c) KNCWS-21.
however, some of the weak/strong functional
groups have disappeared. Nitrogen doping as well
as different activation conditions have resulted in
cm
-1
bandwidth is seen for all samples, indicating
tensile vibration of N-H groups or tensile vibration
of O-H hydroxyl groups of phenol, alcohol, and
carboxylic acid
-1
is related to the asymmetric tensile
vibration of CH
2
, which can be attributed to the -CH-
bond on the carbon surface. -CH- bonds may belong
to alkyl groups such as methyl, methylene groups,
or aldehyde groups
11376 cm
-1
is due to amides, pyridine, and C=N,
indicates nitrogen functional groups at temperatures
higher than crude carbon
-1
is also attributed to the C-N tensile
vibration
3.4. Equilibrium adsorption
Figure 5 shows the performance of both chemical
adsorption processes (nitrogen doping) and
physical adsorption (increasing surface area and
improved the adsorption process. Also, increasing
important role for functional groups, because the
Fig. 4.
Table 1.
Specimens S
BET
D V
tot
V
mic
⁄ V
tot
(m
2
/g) (nm) (cm
3
/g) (%)
KNCWS-11
2461 2.41 1.48 8.78
KNCWS-21
3225 2.48 1.99 10.05
KNCWS-31
2319 2.03 1.17 20.5
36
Anal. Method Environ. Chem. J. 3 (4) (2020) 30-39
Fig. 5.
groups are electron-giving and cause chemical
adsorption. It should be noted that the high share of
and increases adsorption. According to the results
rate of the KNCWS-31 sample is the decrease in
its physical characteristics, which occurred due
to the destruction of the walls between cavities or
blockage of cavities with excessive nitrogen.
According to Table 2, the modulus of adsorption
doped activated nano carbons was consistent with
the Langmuir, Freundlich, and Sips models .
However, the Sips model showed higher values
of R
2
than the Langmuir and Freundlich models
for all samples studied. In this experiment, the
b-constant of the Sips model was approximately
adsorption occurs with a non-uniform distribution
of heat and tensile adsorption across the surface of
doped activated nano table 2.
3.5. Kinetic adsorption
In order to evaluate the speed of the adsorption
process and to determine the process speed control
stage, kinetic modeling is performed. Kinetic
and pseudo-second-order models to provide
a suitable model for the kinetic behavior of the
studied gravity (Fig. 6).
carbons are shown in Table 3
order and pseudo-second-order equations can
predict the adsorption process under experimental
conditions. Given the calculated values of q
e
and R
2
,
2
in the pseudo-
which indicates the reversible adsorption between
4. Conclusion
In this study, a series of nitrogen-doped activated
vapor. In practice, the vapor adsorption capacity
37
Fig. 6.
Table 2.
Isotherms Adsorbents
KNCWS-11 KNCWS-21 KNCWS-31
Langmuir
q
m
348.3383 703.6625 168.2004
b 0.00065812 0.00069629 0.0010431
R-squared 0.99962 0.99824 0.99847
Freundlich
q
m
50.3955 179.2698 23.3665
b 0.0042402 0.0020152 0.009701
n 1.4203 1.4426 1.7413
R-squared 0.99839 0.99586 0.99721
Sips
q
m
232.0382 399.4676 100.7033
b 0.0013378 0.0018034 0.0022754
n 0.78099 0.64366 0.48246
R-squared 1.00000 0.99989 0.99979
Table 3.
adsorption on doped activated nano carbons
Isotherms
KNCWS-11
Adsorbents
KNCWS-21 KNCWS-31
q
e
140.582 295.911 84.529
K
1
0.0309 0.031 0.095
R-squared
0.990 0.982 0.981
pseudo-second-order
q
e
176.946 382.646 0.001
K
2
0.0001 7.603 0.001
R-squared
0.970 0.960 0.995
38
Anal. Method Environ. Chem. J. 3 (4) (2020) 30-39
varies considerably due to their structural and
surface roperties. Nitrogen plays an important
KNCWS-11, KNCWS-21, and KNCWS-31 at
initial concentrations of 1000 ppm have adsorption
rates of 166, 285, and 95 mg g
-1
, respectively.
nano carbons as a green adsorbent provides a cost-
effective means of combating biomass waste and
can partially reduce the climate change caused by
2
at the inlet and
5. Acknowledgments
6. References
455–472.
171–178.
and carbon tetrachloride from gas phase
pretreatment of the adsorbent, Microporous
Mesoporous Mater., 268 (2018) 58–68.
progress in remediation of chlorinated
volatile organic compounds: A review, J. Ind.
use of carbon tetrachloride, tetrachloroethylene,
trichloroethylene and 1,1,1-trichloroethane in
carbon tetrachloride and tetrachloroethylene,
in environment sources, potential human
health impacts, and current remediation
138.
498–502, 2014. https://doi.org/https://doi.
org/10.1016/B978-0-12-386454-3.00436-X.
Cytogenetic analysis of an exposed-referent
study: perchloroethylene-exposed dry
cleaners compared to unexposed laundry
Adsorption performance and mechanism of
perchloroethylene on a novel nano composite
210 (2015) 60–68.
Jafarinejad, A. Rashidi, Lignocellulose-based
adsorbents: A spotlight review of the effective
parameters on carbon dioxide capture process,
Chemosphere, 246 (2020). https://doi.
org/10.1016/j.chemosphere.2019.125756.
from air on metal–organic frameworks
MIL-101(Cr) and MIL-53(Fe) at room
Mater., 28 (2018) 2090–2099.
special reference to the evaluation of surface
(2015) 1051–1069.
Houshmand, A. Arami-Niya, Ammonia
39
oxidation, Appl. Surf. Sci., 257 (2011) 3936–
3942.
A. Rashidi, S. Jafarinejad, Synthesis of
N-doped nanoporous carbon from walnut
shell for enhancing CO2 adsorption capacity
(2018) 6653–6663.
capacity of nitrogen-doped biomass-derived
(2016) 1439–1445.
with eucalyptus wood based activated carbon
513.
impregnated palm shell activated carbon for
CO2 adsorption at elevated temperatures, J.
biochar and the CO2 capture, Bioenergy
Res., 6 (2013) 1147–1153.
C. Zhang, One-step synthesis of microporous
carbon monoliths derived from biomass
with high nitrogen doping content for highly
selective CO2 capture, Sci. Rep., 6 (2016)
4–11.
Ahmed, R. Mohsin, Assessment of porous
carbons derived from sustainable palm solid
waste for carbon dioxide capture, J. Clean.
cherry stone-based carbons in CO2/CH4
257.
Biochem., 34 (1999) 451–465.
Anal. Method Environ. Chem. J. 3 (4) (2020) 40-51
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Solid phase microextraction for organochlorine pesticides
electron capture detector
Hamideh Assadollahzadeh
a,*
and
Ebrahim Noroozian
b
a
Department of Chemistry, Kerman Branch, Islamic Azad University, Kerman, Iran, P. O. Box 7635131167.
b
Department of Chemistry, Shahid Bahonar University of Kerman, P.O. Box 133-76175, Kerman, Iran
ABSTRACT
received an increasing attention in the last decades. solid-phase
which has been widely used for the determination of volatile and
semivolatile organic compounds in aqueous samples. In this study,
temperature, ionic strength, desorption time, and desorption
-1
, the inter-
ranges varied between 0.001 and 1 ng mL
-1
was successfully applied to the analysis of ground water samples with
the recoveries from 86 to 110%
Keywords:
Organochlorine pesticides,
Multiwalled carbon nanotubes,
Solid phase microextraction,
Gas chromatography
ARTICLE INFO:
Received 18 Aug 2020
Revised form 15 Oct 2020
Accepted 23 Nov 2020
Available online 29 Dec 2020
*Corresponding author:
https://doi.org/10.24200/amecj.v3.i04.117
------------------------
1. Introduction
widely used worldwide in order to increase crops
output and enhance quality of products. But most of
these compounds have been eliminated or restricted
in use after evidence of their toxicity and persistence
in the environment . For determination of trace
a high number of interfering compounds, usually
and high performance analytical instruments. Sample
preparation before chromatographic analysis is one
of the most important steps in analytical processes.
. Although these
of a large amount of expensive and toxic solvents
is also time-consuming, tedious, and very often
requires solvent evaporation prior to introduction
41
of the sample into the analytical instrument. Solid-
phase extraction also has certain drawbacks, such
as plugging of cartridges, solvent consumption for
conditioning and elution steps and lack of elution
selectivity. Alternative methods, such as dispersive
, single-
, membrane-
,
have
and reduce solvent consumption, etc. However,
is a practical
solvent-free alternative for the extraction of organic
meaningfully
decreases the analysis time. In this method, analytes
are generally extracted and concentrated by a thin
is then introduced into a chromatographic system
sampling, extraction, concentration and sample
introduction into a single solvent-free step.
Currently, the improvement in the applications
coatings are include polyaniline , polythiophene
, polypyrrole , metalorganic frameworks
(MOFs) , layered double hydroxide (LDH)
, metal and metal oxide , molecularly
, carbon nanotubes
. A multiwalled carbon nanotube-polypyrrole
of phthalate esters from water . In the present
water.
2. Experimental
2.1. Chemicals
endrin, endosulfan I, endosulfan II, p,p’-DDD, o,p-
was obtained from Merck (Darmstadt, Germany,
http://www.merck.com) and was distilled and
stored in a dark bottle under nitrogen atmosphere
in a refrigerator. Multiwalled carbon nanotubes
(Berlin, Germany, http://www.plasmachem.com)
was 20-40 nm in diameter and 1-10µm in length.
Stainless Steel wire (type 100-014, 350µm O.D.)
was obtained from (Carlsbad,
-1
stock solution
Working solutions were prepared by appropriate
dilution of the stock solution in distilled water.
respectively. Other reagents used were of highest
purity available. Double distilled water was used in
all experiments.
2.2. Apparatus
a 23 gauge, 9.0-cm stainless steel spinal needle Dr.
com), housed in a 6.0-cm hollow cylinder of Al with
two nuts and two pieces of rubber septum. A 17-cm
piece of the stainless steel wire passing through the
was attached to a cap and 3 cm of the other end was
coated with
Behpajuh
electrode used in the electrochemical process were
For stirring and
was used.
42
Anal. Method Environ. Chem. J. 3 (4) (2020) 40-51
chromatograph (Kyoto, Japan, http://www.
gas and nitrogen make-up gas were adjusted at l mL
min
-1
and 30 mL min
-1
-1
-1
GC-MS instrument (Kyoto, Japan, http://www.
Bandelin Sonorex ultrasonic bath (Berlin, Germany,
http://www.bandelin.com) was use for sonication.
2.3. Preparation of composite coating
s-COOH was collected
composite coating of polypyrrole
Stainless steel wire, platinum electrode and Ag/
AgCl electrode were used as working, counter
was ultrasonically dispersed in water for 1h at 28
min. coating was directly
deposited on the steel wire from this solution by
paper and then washed in acetone while sonicating.
chromatographic baseline is obtained.
2.4. SPME procedure
A 0.1 ng mL
-1
working solution of the mixture of
performed by placing 10.0 mL samples into a 12.0
mL sample vial capped with a septum. Magnetic
was used to agitate the samples at the highest but
out by exposing a 3.0 cm length of the composite
temperature was adjusted by placing the extraction
vial in a water bath placed on the magnetic stirrer.
the needle, removed from the sample vial and
immediately introduced into the GC injector port for
thermal desorption.
3. Results and discussion
3.1. SPME optimization
In this study, the effect of various parameters on the
and temperature, salting out effect, pH, extraction
time and extraction temperature were studied on a
one-at-a-time strategy. Stirring the sample during
to generate a continuously fresh layer of the sample
layer and thus improves the speed of extraction.
under maximum but constant stirring rate.
3.1.1.Desorption time and desorption temperature
Study of desorption processes can provide useful
information on the absorbent and the absorption
processes. Desorption of extracted analytes was
carried out in the GC injection port at temperatures
Figure 1 shows that at
43
subsequent experiments a desorption temperature of
studied. For this purpose, desorption times between
1 and 20 min were used After a desorption time
or carry over an extra 5.0 min was considered in
Fig. 1.
-1
Fig. 2.
-1
44
Anal. Method Environ. Chem. J. 3 (4) (2020) 40-51
carried out for a period of 10 min (Fig. 2).
3.1.2. Extraction time
involving partitioning of the analytes from the
sample liquid phase to the sorbent phase on the
of analytes should be overcome to reach equilibrium
ng mL
-1
each)
shown in Figure 3.
areas sharply increase with increases in the extraction
50 min was selected as the extraction time.
3.1.3. Extraction temperature
Fig. 3
-1
45
parameter. An increase in the extraction temperature
the same time a decrease in distribution constant,
leading to faster extraction, but reduced extraction
extraction temperature was varied between 20 and
Figure 4
these analytes. In some cases, at temperatures above
the distribution constant at these temperatures
chosen as the optimum extraction temperature for
all subsequent analyses.
3.1.4. Ionic strength
Ionic strength can vary the mechanism of mass
structure, analyte properties and matrix . In
addition, the solubility of the non-polar organic
solutes in water decreases in the presence of salts.
Fig. 4.
-1
extraction
no sample pH and salt was adjusted or added.
46
Anal. Method Environ. Chem. J. 3 (4) (2020) 40-51
reason, the effect of this parameter on extraction
carried out from solutions in the presence of NaCl
from 0 to 20% (w/v). Figure 5 shows that for most
improvement in the extraction
higher NaCl concentrations.
by the fact that the present composite coating is a
solid porous sorbent, and the extraction occurs on
the surface of pores. It seems that large amounts of
NaCl in the sample solution occupies the surface of
the coating material and have a negative effect on the
it was decided to carry out all subsequent extractions
without adding any salt to sample solutions.
Fig. 5.
-1
desorption time=10
no sample pH adjusted.
3.1.5. pH optimization
Further investigations were carried out on pH value
out using the original solution.
3.2. Method Validation
Figures of merit including linear range (LR),
precision (RSD %) and limit of detection (LOD)
were evaluated for the method developed in
extracting a series of aqueous solutions of the
1.0 ng mL
-1
for lindane and heptachlor, 0.01 to
1 ng mL
-1
-1
endrin + p,p’-DDD, endosulfan II, o,p-DDD and
47
of determination (r
2
of the method was determined by seven replicate
analyses from mixed aqueous solutions containing
0.02 ng mL
-1
intra-day relative standard deviations (RSD%)
varied from 3.6 % for lindane to 11.5 % for
endosulfan II, while the inter-day RSD% varied
from 6.5% for methoxychlor to 11.5% for dieldrin.
0.39 pg mL
-1
(Table 1).
of the method, a water sample was collected from
the university campus and subjected to the present
No pesticide was detected in this sample using
sample was used as blank and spiked at 0.01 and
0.075 ng mL
-1
found were reasonable and between 86 and 110%
(Table 1).
here were compared with results obtained by other
methods which show that they are comparable or
better than the values reported by other groups
(Table 2).
Table 1. Analytical performance : Limit of detection (LOD), percent recovery,
2
) and RSD%.
Compound
LOD
(pg mL
-1
)
Recovery (%)
LR
(ng mL
-1
)
Coeff. Det
RSD%
0.01 0.075
ng mL
-1
ng mL
-1
r
2
Intra-day
(N=7)
Inter-day
(N=7)
Lindane 0.08 91 103 0.001 - 1 0.9958 3.6 6.8
Heptachlor 0.17 89 94 0.001 - 1 0.9926 8.6 8.1
Aldrin 0.11 89 93 0.005 - 1 0.9879 8.8 10.1
0.18 95 93 0.005 - 1 0.9954 5.2 7.1
0.16 86 89 0.005 - 1 0.9938 8.6 9.5
0.17 105 101 0.005 - 1 0.9894 7.3 9.8
Dieldrin 0.095 95 88 0.005 - 1 0.9871 6.2 11.5
0.065 92 94 0.005 - 1 0.9940 11.5 11.1
o,p’-DDD 0.051 106 101 0.005 - 1 0.9932 9.8 9.4
0.39 110 98 0.05 - 1 0.9976 7.5 9.2
Methoxychlor 0.1 102 98 0.005 - 1 0.9979 6.8 6.5
48
Anal. Method Environ. Chem. J. 3 (4) (2020) 40-51
Table 2.
analysis based on
Compound References
a
b
c
Lindane 0.08
d
0.3 0.25 3.8 5 0.2 0.34
3.6
e
6 5.6 3.7 5.1 7.1 7.1
Heptachlor 0.17 1.6 0.27 2.7 10 - 0.32
8.6 3 4.7 4.2 12.4 - 6.7
0.16 0.6 0.125 3.7 51 - 3.4
8.6 6 8.7 3.7 14.6 - 10.2
p,p’-DDD 0.16 - 0.095 - 2 - -
8.6 - 6.3 - 7.3 - -
Aldrin 0.11 0.2 0.66 2.6 14 - 0.39
8.8 3 9.6 3.9 35.3 - 8.1
0.17 0.1 0.015 5.7 1 - 0.33
7.3 8 9.1 5.7 15.3 - 9.6
Dieldrin 0.095 0.1 0.015 2.8 9 0.5 0.36
6.2 12 9.1 3.8 11.5 7.7 8.9
0.065 0.1 0.051 3.6 18 1 1.41
11.5 10 6.5 4.3 11.2 7.8 12.1
o,p’-DDD 0.051 - 0.24 - - - -
9.8 - 9.7 - - - -
0.39 0.1 0.26 3.7 13 - 0.34
7.5 5 7.3 3.7 14.7 - 8.2
0.18 0.1 0.17 2.9 10 0.8 1.29
5.2 4 8.3 4.3 10.8 5.8 11.2
Methoxychlor 0.1 - 0.048 - - - 0.26
6.8 - 7.3 - - - 11.8
a
: Full scan MS
b
: MS/MS
c
: Membrane-protected micro-solid-phase extraction
d
)
e
49
3.3. Real samples
four water samples were collected and stored in
shown in Table 3. None of the organochlorine
pesticides were detected in the samples collected
from the campus of Shahid Bahonar University
(SBUC) and Saadi village, but the two samples
from Noogh and Zarand area were found to be
contaminated.
based on
Table 3. analysis in real samples based on by
Location
Noogh Saadi Zarand SBUC
Compound
Concentration (pg mL
-1
)
Lindane N.D N.D N.D N.D
Heptachlor N.D N.D N.D N.D
Aldrin N.D N.D N.D N.D
N.D N.D N.D N.D
o,p-DDD 8.6 N.D N.D N.D
Dieldrin N.D N.D N.D N.D
65 N.D 54 N.D
11 N.D 7.3 N.D
N.D N.D N.D N.D
Methoxychlor N.D N.D N.D N.D
8 N.D 6.1 N.D
N.D: not detected
4. Conclusions
from water samples was successfully performed
sensitive, precise, reproducible and linear over
a wide range. Due to the widespread use of the
organochlorine pesticides until 1970’s and the high
persistence of these pollutants can still be detected
some of these in the environment.
method showed good reproducibility, wide linear
range, low detection limit and good recovery for
5. Acknowledgement
Department of Chemistry,
Shahid Bahonar University of Kerman, Iran
6. References
Article, Organochlorine pesticides, their
toxic effects on living organisms and their
9 (2016) 90-100.
Application of multiwalled carbon nanotubes
for the preconcentration and determination of
50
Anal. Method Environ. Chem. J. 3 (4) (2020) 40-51
organochlorine pesticides in water samples by
gas chromatography with mass spectrometry,
J. Sep. Sci., 39 (2016) 4219-4226.
persistent organochlorine pesticides and
their mobility in the environment, Curr. Org.
Chem., 22 (2017) 954-972.
Alhooshani, Ionic liquid-based membrane-
protected micro-solid-phase extraction of
organochlorine pesticides in environmental
water samples, Microchem. J., 158 (2020)
105295.
Alonso, Liquid-liquid extraction followed by
solid phase extraction for the determination
of lipophilic pesticides in beeswax by
gas chromatography electron capture
detection and matrix matched calibration, J.
Chromatogr. A, 1048 (2004) 89-97.
determination of organochlorine pesticides
based on dynamic microwave-assisted
extraction coupled with on-line solid-
phase extraction of high performance liquid
chromatography, Anal. Chim. Acta, 589
(2007) 239-246.
Recent developments of dispersive liquid
liquid microextraction technique, Chinese J.
Chromatogr., 33 (2015) 103-111.
439-472, 2019.
solid-phase extraction: A review of features,
advancements and applications, Anal. Chim.
Acta, 965 (2017) 36-53.
Dispersive solid phase microextraction,
809.
Nakamura, Fast screening of pesticide
multiresidues in aqueous samples by dual stir
bar sorptive extraction-thermal desorption-
low thermal mass gas chromatography-mass
spectrometry, J. Chromatogr. A, 1130 (2006)
83-90.
the extraction of organics from water matrix
samples and their rapid transfer to capillary
(1989) 179-191.
microextraction of organochlorine pesticides
from water, J. Sep. Sci., 31 (2008) 2839-
2845.
of thermally stable nano-structured self-
doped polythiophene coating for analysis of
phthalate ester trace levels, J. Sep. Sci., 35
(2012) 563-570
determination of haloanisoles in water and
wine, Anal. Methods, 8 (2016) 5503-5510.
of organochlorine pesticides in water, Anal.
Chim. Acta, 638 (2009) 169-174.
organic framework@microporous organic
network as adsorbent for solid-phase
microextraction, Anal. Chem., 88 (2016)
9364–9367.
onto a stainless steel wire for direct-
immersion solid-phase microextraction of
51
polycyclic aromatic hydrocarbons prior to
their determination by GC-FID, Microchim.
Acta, 185 (2018) 341.
solid-phase microextraction coatings for
determining organochlorine pesticides in
aqueous environmental samples, J. Sep. Sci.,
40 (2017) 2009–2021.
Chem., 75 (2016) 174-182
Highly sensitive and selective hyphenated
technique (molecularly imprinted polymer
solid-phase microextraction-molecularly
imprinted polymer sensor) for ultra trace
analysis of aspartic acid enantiomers, J.
Chromatogr. A, 1283 (2013) 9-19.
microextraction of organochlorine pesticides
in lake water and wastewater, J. Sep. Sci., 30
(2007) 2138-2143.
Synthesis of carbon nanotube/layered
double hydroxide nanocomposite as a novel
microextraction of phenols from water
samples, J. Sep. Sci., 38 (2015) 1344-1350.
Maghsoudi, Solid phase microextraction
of phthalate esters from aqueous media by
electrochemically deposited carbon nanotube/
polypyrrole composite on a stainless steel
1997.
Determination of organochlorine pesticides
by gas chromatography with solid-phase
microextraction, Chromatographia, 56 (2002)
191-197.
phase microextraction gas chromatography-
(tandem) mass spectrometry as a tool for
pesticide residue analysis in water sample
at high sensitivity and selectivity with
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Anal. Method Environ. Chem. J. 3 (4) (2020) 52-59
Research Article, Issue 4
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Dispersive solid phase extraction using graphitic carbon
nitride microparticles for the determination of trace amounts
of lead in water samples
Ehsan Zolfonoun
a,*
a
Nuclear Fuel Cycle Research School, Nuclear Science and Technology Research Institute, Tehran, Iran
ABSTRACT
In this work, ultrasound-assisted dispersive micro-solid phase
(g-C
3
N
4
) is proposed for the preconcentration of low level of lead
carbon nitride sorbent were dispersed in the samples using ultrasonic
bath and ions were directly adsorbed on the surface of g-C
3
N
4
particles. After adsorption and desorption of lead ions from g-C
3
N
4
advantages of this method are high speed, simplicity and cheapness.
L
-1
procedure.
Keywords:
Lead, Graphitic carbon nitride,
Water,
Ultrasound-assisted dispersive mi-
cro-solid phase extraction,
Inductively coupled plasma- optical
emission spectroscopy
ARTICLE INFO:
Received 6 Sep 2020
Revised form 10 Nov 2020
Accepted 28 Nov 2020
Available online 30 Dec 2020
*Corresponding author:
https://doi.org/10.24200/amecj.v3.i04.118
------------------------
1. Introduction
With the development of various industries over the
past decades and increasing the amount of pollut-
ants entering the environment, the amount of heavy
metals in soil and water increased . Most of these
heavy metals are not only environmentally destruc-
-
-
hibition and nervous connection damages are the
most important toxic effects of lead on human .
-
al is its accurate measurement. For this purpose,
various analytical techniques have been developed
. In all of the reported analytical techniques,
sample preparation (separation and preconcentra-
tion) step is needed prior to instrumental analysis.
Among different sample preparation methods, sol-
id phase extraction is the most common one due
to its unique features such as simplicity, low cost,
high recoveries and low consumption of organic
solvents .Dispersive micro solid phase ex-
advantages of both dispersive liquid-liquid micro-
extraction and solid phase extraction . In this
method a mixture of sorbent particles and carrier is
injected to the aqueous sample. After formation of
cloudy solution, extraction can be achieved with-
in a few seconds because of the large surface area
53
between extraction sorbent and aqueous phase .
analytical chemistry because it is a simple, fast and
inexpensive method . One of the most im-
portant parameters that affect the performance of
this method is the type of sorbent -
have been demonstrated in recent reports .
-
erties of nanoparticles have made them suitable
-
ferent nanosorbents, cheaper and more stableones
such as graphene and carbon nanotubes have been
used more frequently . Graphitic carbon ni-
tride (g-C
3
N
4
) is a non-toxic analogue of graphene
which is very stable and inexpensive and has suit-
able band structure, easy synthesis method and
unique physicochemical properties . It has
from various simple and green nitrogen rich precur-
sors such as melamine, thiourea, urea, cyanamide
structure and polar functional groups , g-C
3
N
4
can
be a suitable and ecofriendly candidate for conven-
tional sorbents in extraction methods .
In the current study, we propose a simple, fast and
ligandless preconcentration technique based on
ultrasound-assisted dispersive micro-solid phase
nitride for the determination of lead by inductively
coupled plasma-optical emission spectrometry.
2. Experimental
2.1. Reagents and materials
All chemicals used in this work were of analytical
grade. All aqueous solutions were prepared in dou-
-
lipore, USA).
Merck (Darmstadt, Germany).-
2+
) was purchased with a concen-
tration of 1000 mg L
-1
in 1 % HNO
3
. Another con-
centration of lead was daily prepared by dilution
of the standard lead solution with DW. Ultrapure
water was purchased from Millipore Company.
3
N
4
-
carbon nitrides ( g-C
3
N
4
of a mixture of melamine with the formula C
3
H
6
N
6
and uric acid ( C
5
H
4
N
4
O
3)
in the presence of crys-
talline form of alumina (Al
2
O
3
) has been reported.
Alumina favored the deposition of the graphitic
carbon nitrides layers on the exposed surface .
2.2. Instrumentation
-
tector (CCD) and a cyclonic spray chamber with a
lead was 220.353 nm. A Metrohm model 744 digital
pH meter, equipped with a combined glass-calomel
electrode, was employed for the pH measurements.
An ultrasonic water bath with temperature control
-
fuge accessory based on the rotor with high speed
(speed 2000-30.000 rpm x g, Sigma 3K30 centri-
fuge, UK) was used for separation nanoparticles
from water samples. For sampling, all glass tubes
were cleaned with a 1.0 mol L
-1
HNO
3
solution for
-
pared and stored by standard method for sampling
from water by adding nitric acid to waters.
2.3. On-line extraction procedure
Due to Figure 1, 6.0 mg of g-C
3
N
4
was added to 10
mL of water sample or standard solution and soni-
cated by an ultrasonic bath for 5 min.
and physical adsorption of lead ions carried out by
g-C
3
N
4
.
lead ions with g-C
3
N
4
, the solution was then cen-
trifuged for 5 min at 5,000 rpm, and the aqueous
-
alyte was eluted using 1.0 mL of a 1 mol L
solu-
tion of HNO
3
54
Anal. Method Environ. Chem. J. 3 (4) (2020) 52-59
g-C
3
N
4
nanostructure with lower and upper limit
) for lead analysis in
water and standard samples by ultrasound-assisted
dispersive micro-solid phase extraction (USA-D-
.
3. Results and discussion
3
N
4
as
adsorbent was used for the extraction and separa-
tion of lead ions in water samples. In order to obtain
the favorite lead speciation with high extraction,
adsorbent, the sonication time, the eluent type and
3.1. Effect of pH
important factors in metal–adsorbent interac-
the extraction of by g-C
3
N
4
was studied in
the range of 3.0–8.0 using nitric acid or sodium
Figure 2 show that the
adsorption of is maximum in the pH range
of 6.0 to 7.5. So, pH 6.0 was chosen as the opti-
achieved based on the coordination of covalent
bond of N in g-C
3
N
4
with the positively charged
2+
), which is highly dependent
3.2. Effect of g-C
3
N
4
amount
3
N
4
on the quantitative
1–10 mg by ultrasound-assisted dispersive mi-
-
sults are shown in Figure 3
revealed that by increasing the sorbent amounts
from 1 up to 6 mg, due to increasing accessible sites,
-
mained constant. Hence, the subsequent extraction
experiments were carried out with 6 mg of g-C
3
N
4
.
3.3. Effect of sonication time
analytes extraction. By favorite time for solid dis-
persion in liquid phase, the mass-transference was
based on the g-C
3
N
4
was obtained in water sam-
-
traction and recovery of was studied in the
from 5 to 20 min. So, an ultrasonication time of 5
min was selected for the entire procedure.
3.4. Effect of eluent type
lead ions from g-C
3
N
4
Fig.1. On-line extraction procedure for lead extraction by g-C
3
N
4
particles
55
Low pH caused to dissociate N-lead bonding and
-
ent acid solution such as HCl, HNO
3
, H
2
SO
4
, and
CH
3
COOH with different concentration was used
mol L
-1
that among the tested eluents, nitric acid
was the
superior striping agent for the quantitative elution
of
3
solution was selected
for
con-
Fig. 2.
3
N
4
amount,
–1
.
Fig. 3.
3
N
4
concentration of analyte, 50 µg L
–1
.
56
Anal. Method Environ. Chem. J. 3 (4) (2020) 52-59
centration on the recovery of the adsorbed analyte
was studied in the range of 0.1 to 3 mol L
. Based
on the obtained results, 1.0 mol L
HNO
3
was suf-
from the sorbent surface (Fig.4).
3.5. Effect of diverse ions on the recovery
In order to evaluate the analytical applicability of
the developed method, the effect of commonly
occurring ions in natural water samples on the ex-
traction and determination of lead was studied. In
these experiments, 10 mL of sample solutions con-
taining
of various amounts
of interfering ions were treated according to the
recommended procedure.
as the highest amount of foreign ions which cause
an approximately ± 5 % relative error in the de-
termination of the analyte.
40,000-fold Li
+
, Na
+
, K
+
, Cl
-
, NO
3
-
, 20,000-fold
Ca
2+
, Mg
2+
, Ba
2+
, Sr
2+
, 400-fold Ag
+
, Cd
2+
, Co
2+
,
Zn
2+
, Mn
2+
, 200-fold Fe
3+
, Ni
2+
, Cr
3+
, Ce
3+
, and 100-
fold Al
3+
, Cu
2+
, Hg
2+
-
3.6. Analytical gures of merit
-
marised in Table 1. Linear working range of the
5.0–600 µg L
proposed method was calculated as three times the
standard deviation of 10 measurements of the blank
be 1.24 µg L
(R.S.D) of the proposed method for determination
of 50.0 µg L
Table 1. Analytical parameters of the proposed method
Parameter Analytical feature
Linear range (µg L
) 5.0–600
r
2
0.998
LOD (ng L
) 1.24
R.S.D. % (n = 10) 2.3
10
Fig.4. based on g-C
3
N
4
particles
57
3.7. Application
analytical results, along with the recovery for the
spiked samples, are given in Table 2
values calculated for the spiked samples were in
-
can be used as a reliable
sample treatment technique for extraction and de-
were used for validating of proposed procedure by
g-C
3
N
4
nanostructure in water and urine samples
(Table 3).
4. Conclusions
A preconcentration technique based on ultrasound-as-
sisted micro-solid phase extraction using graphitic
carbon nitride microparticles was developed for the
extraction and preconcentration of from aque-
ous samples,
proposed method there is no need to use any chelat-
-
posed method gives a high enhancement factor and
low LOD and can be used for the preconcentration
and determination of lead in real water samples.
5. Acknowledgements
-
Table 2. Recovery of lead from water samples based on g-C
3
N
4
Sample Added (µg L
−1
) Found (µg L
−1
) Recovery (%)
0.0 <LOD –
10.0 10.2 (2.5)
a
102
Well water 0.0 5.1 (3.2) –
10.0 14.5 (3.0) 94
River water 0.0 4.3 (2.9) –
10.0 14.8 (2.6) 105
a
Table 3.
Recovery (%)
Found
*
( μg L
-1
)Added( μg L
-1
)SRM( μg L
-1
)
Sample
-----17.4 ± 0.9-----18.2 ± 0.6
a
SRM1643d
96.631.9 ± 1.415.0
-----138.6 ± 6.5-----137.9 ± 3.6
b
SRM 2668
99.4287.7± 11.4150.0
*
a
SRM1643d, trace element in water
b
-1
Anal. Method Environ. Chem. J. 3 (4) (2020) 52-59
6. References
injection preconcentration of lead and cad-
mium using cloud point extraction and de-
termination by atomic absorption spectrom-
-
tration of Lead in Blood and Urine Samples
-
of lead with Amberlite XAD-2 and Amber-
lite XAD-7 based chelating resins for its
-
uid-dispersive liquid phase microextraction
for determination of trace lead level in blood
absorption spectrometry with multivariate
5–10.
of a robust ionic liquid-based dispersive
liquid–liquid microextraction against high
concentration of salt for preconcentration of
trace metals in saline aqueous samples: Ap-
Anal. Chim. Acta, 669 (2010) 25-31.
M. Salavati-Niasari, Separation and precon-
centration of trace gallium and indium by
Amberlite XAD-7 resin impregnated with
a new hexadentates naphthol-derivative
1851-1868.
Kaminska, B.M. Stel’makhovych, A sol-
id-phase extraction method using acid-mod-
-
concentration of trace amounts of lead in
water samples, Appl. Nanosci., 9 (2019)
1057-1065.
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persive micro-solid phase extraction,
226-233.
-
banian, Deep eutectic solvent magnetic
bucky gels in developing dispersive solid
phase extraction: Application for ultra trace
analysis of organochlorine pesticides by
-
of dispersive micro-solid phase extraction
-
walled carbon nanotubes as solid sorbent
in dispersive micro solid-phase extraction
for the sequential determination of cadmi-
um and lead in water samples, Microchem.
J., 126 (2016) 296-301.
Dispersive micro-solid-phase extraction
based on polyaniline/magnetic nanopar-
ticles composite, Anal. Chim. Acta, 844
(2014) 80-89.
nanoparticles based dispersive micro-sol-
id-phase extraction as a novel technique
for the determination of estrogens in pork
samples, Food Chem., 204 (2016) 135-
140.
determination of indium using multiwalled
carbon nanotubes modified with magnet-
Chem. J., 1 (2008) 5–10.
Cu
2
O-CuO ball like/multiwalled carbon
nanotube hybrid for fast and effective ul-
trasound-assisted solid phase extraction of
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mination of L-tryptophan after preconcen-
tration using multi-walled carbon nano-
(2019) 43-48.
Fe
3
O
4
@graphene oxide core-shell nano-
spheres for ferrofluid-based dispersive
solid phase extraction as exemplified for
Cd(II) as a model analyte, Microchim.
Acta, 183 (2016) 1749-1757.
-
tube-based magnetic bucky gels in devel-
oping dispersive solid-phase extraction:
application in rapid speciation analysis of
1079.
X. Chen, Facile preparation and applica-
tions of graphitic carbon nitride coating in
solid-phase microextraction, J. Chromato-
gr. A, 1364 (2014) 53-58.
a graphitic carbon nitride nanocomposite
with magnetite as a sorbent for solid phase
extraction of phenolic acids, Microchim.
Acta, 182 (2015) 737-744.
Chen, Simple pyrolysis of urea into gra-
phitic carbon nitride with recyclable ad-
sorption and photocatalytic activity, J. Ma-
ter. Chem., 21 (2011) 14398-14401.
magnetic carbon nitride nanosheets and
its application in magnetic solid phase
extraction for polycyclic aromatic hydro-
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Anal. Method Environ. Chem. J. 3 (4) (2020) 60-71
Research Article, Issue 4
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Determination and investigation of heavy metal
evaluation of their potential environmental risk
Hoda Allami
a
, Afsaneh Afzali
a,*
and Rouhollah Mirzaei
a
a
Department of Environment, Faculty of Natural Resources and Earth Sciences, University of Kashan, Kashan. Iran
ABSTRACT
caused to a serious concern due to their environmental consequences.
ports in Bushehr province. In this regard, the sampling was performed
in 10 stations with different uses in two depths of 0-5 and 5-20 cm
metals was measured after drying, acid digestion and microwave by
index was used to assess the potential of environmental risk due to
heavy metal pollution in the coastal sediments of the study area and
in surface sediments, and 131.59, 10.81, 12.56 and 4.88 µg g
-1
in deep
less than 150, showed a low environmental risk of heavy metals
detected in the region. Also, the results of multivariate statistical
of Cu, Ni and Mn. In general, this study led to a better understanding
of the contamination of heavy metals in the region and considered it
necessary to try to prevent, control and reduce the amount of pollution
dilution samples with DW.
Keywords:
Heavy metals,
Analysis,
Flame/electrothermal atomic
absorption spectrometry,
ARTICLE INFO:
Received 22 Aug 2020
Revised form 20 Oct 2020
Accepted 15 Nov 2020
Available online 30 Dec 2020
*Corresponding Author:
https://doi.org/10.24200/amecj.v3.i04.122
------------------------
1. Introduction
Heavy metals as the inorganic pollutants are con-
sidered as one of the serious threats in natural
ecosystems due to their non-degradability, the
environmental stability, the toxicity to various
.
Heavy metal pollution results from rapid urban-
generation, transportation, fossil fuel combus-
tion, use of various chemicals, and other related
activities . Heavy metals are metals with a
-2
. In the
61
aquatic ecosystem, a number of metals such as
Zn, Fe, Mn and Ni are required for the activity of
biological systems. For example, diseases such as
skin diseases are the result of removing essential
-
ings. However, the high concentrations of heavy
metals can be toxic to human organisms. While
are not essential for the activity of biological sys-
tems, their presence in aquatic ecosystems causes
toxicity to living organisms . Also, some met-
to their toxic and carcinogenic properties. In ad-
enters the environment through human activities
from natural sources, the high concentration of
this metal in the environment can be considered
as an indicator of the level of pollution caused
by human activities in the region . Coastal
areas are the point of connection between land
and ocean, which are more important than other
marine habitats due to their ecological sensitivity
to pollutants, transmission of contaminants in the
food chain and poisoning of living organisms .
Since the beginning of the industrial revolution
and the subsequent increase in industry growth,
the large amounts of toxic pollutants have been
discharged into the coastal environment, causing
metal pollution of the sediments. Heavy metals
in the coastal environment originate from two
natural and human sources . Metal contam-
inants in coastal sediments are precipitated by
adsorption, hydrolysis, and co-sedimentation,
while a small fraction of free metal ions remain
in the water column. However, when environ-
mental conditions such as pH change, the metals
in the sediment enter the water, as a result, the
sediments can also act as a secondary source of
metals . Since more than 90% of heavy met-
al pollution entering the marine ecosystem orig-
inates from terrestrial sources , the coastal
sediments are often referred to as heavy metal
reservoirs or inlets . Some researchers have
been performed to investigate and identify the
concentration of heavy metals and evaluation of
their potential environmental risk on the coastal
area i.e on the coastal sediments of Kerala, India
, on the surface sediments along the southeast
coast of the Caspian Sea , on surface sedi-
ments of the Sobi Shoal, China and on the
-
sian Gulf
index in the study of Arfaeinia et al. (2019) on
that the industrial, agricultural, urban and natu-
ral areas are in the category of very high, con-
siderable, moderately and low environmental risk
levels, respectively. Due to the lack of data on
the abundance and distribution of heavy metals
in sediments of the coastal areas of the world, es-
consequences of these pollutions, especially their
negative impact on marine ecosystem and the life
of living things, further studies on the extent of
-
spectrometry (F-AAS), inductively coupled plas-
inductively coupled plasma mass spectrome-
determination heavy metals in water, industrial
matrixes in biological, industrial wastewater and
sediment samples sample preparation based on
-
-
gestion was used before determination of heavy
metals by instruments.
due to its high biodiversity, rich natural resourc-
es, warm climate and natural attractions, attracts
millions of tourists annually. Consequently, the
discharge of municipal and industrial wastewa-
ter has caused the presence of various pollutants,
including heavy metals in the sediments of this
area the objective of this study is to measure
the concentration of heavy metals in the coasts
62
Anal. Method Environ. Chem. J. 3 (4) (2020) 60-71
estimate the extent of heavy metal pollution and
evaluation of their potential environmental risk
in the region. All heavy metals were determined
by microwave digestion/acid digestion coupled to
F-AAS.
2. Experimental
2.1. Instrumental
-
el(Ni) and manganese (Mn) was performed with
-
mination in surface and deep sediments samples
(GBC, model plus 932, Aus). Copper based on
wavelength 324.7 nm, slit 0.5 nm, lamp current
3.0 mA (1-5 mg L
-1
), lead based on wavelength
217.0 nm, slit 1.0 nm, lamp current 5.0 mA (2.5-
20 mg L
-1
), nickel with wavelength 232.0 nm, slit
0.2 nm, lamp current 4.0 mA (1.8-8 mg L
-1
) and
manganese by wavelength 279.8 nm, slit 0.2 nm,
lamp current 5.0 mA (1-36 mg L
-1
) were selected.
-
using a graphite furnace module (GF3000, GBC)
parameters for the metal of interest were set as
light of hollow cathode lamp (GBC) adjusted
on the furnace tube or burner. All samples were
and temperature programming for the graphite at-
Table 1a and 1 b.
2.2. Reagents
All reagents were of analytical grade from Merck
and manganese (Mn) stock solution was prepared
from an appropriate amount of the nitrate salt of
this analyte as 1,000 mg L
-1
solution in 0.01 mol
L
-1
HNO
3
(Merck). Standard solutions were pre-
pared daily by dilution of the stock solution. Ul-
-
lipore Continental Water System (Bedford, USA).
2.3. Area of study
with an area of about 226,000 square kilome-
subtropical climate with a minimum water ex-
change and an average depth of 35-40 meters.
-
Table 1a. Instrumental conditions for heavy metal determination by F-AAS
NiMnCu
232.0 nm
0.2 nm
4.0 mA
Automatic
1.8-8
279.8 nm
0.2 nm
5.0 mA
Automatic
1-36
217.0 nm
1.0 nm
5.0 mA
Automatic
2.5-20
324.7 nm
0.5 nm
3.0 mA
Automatic
1-5
Wavelength (nm)
Slit (nm)
Lamp current (mA)
Injection mode
Working range (mg L
-1
)
Mode
Table 1b.
Ar ow rate
(mL min
−1
)
Hold
time (s)
Ramp time
(s)
Temperature
Ni (
◦
C)
Temperature
Mn (
◦
C)
Temperature
Pb (
◦
C)
Temperature
Cu (
◦
C)
Step
3001020130130120120Drying
3001040900700400800Ashing
0.0212400240020002300
300312600260022002500Cleaning
63
low depth, high water temperature and salinity
have caused the Contaminants remain stable
in this area for a long time. Kangan port with
a population of 60187 people is located in the
south of Bushehr province and on the coast of
-
has been agriculture, fishing and marine trade.
Also, Siraf port with a population of 6992 people
is in the central part of Kangan city in Bushehr
province.
and Assaluyeh ports and has a special character-
istic due to its location between the two regions
and Kangan energy region.
Also, the its historical area and the beautiful sea
each station and the geographical coordinates of
the sampling points are presented in Table 2 and
shown in Figure 1.
Table 2. Geographical coordinates of sampling stations
Geographical coordinates
Station locationStation name
X
3059458635084
Siraf port
S
1
3059481634398S
2
3060955632126S
3
3075796607211
Kangan port
K
1
3079199603885K
2
3079640603295K
3
3080053602444K
4
3080147601383K
5
3080150600489K
6
3080196599667K
7
Fig. 1. Location of the study area and sampling stations
Anal. Method Environ. Chem. J. 3 (4) (2020) 60-71
2.4. Sampling method
In order to determine the concentration of heavy
metals, sampling was performed in January
2018. For sampling, 10 stations were selected
where sediment has the most contact with wa-
ter. Accurate sampling points were determined
Coastal sediments were collected in the lower
tidal line in a transect with a length of 1000 m
using 30 x 30 cm quadrats in three replications
and two depths of 0-5 and 5-20 cm. During sam-
pling, natural waste pieces such as wood and
stone were removed from the sampling area.
-
lected from each station using a stainless steel
shovel and metal ruler from the surface and
subsurface layer. Samples collected from both
depths were placed separately in sealed bags
and transferred to the laboratory after number-
dried at room temperature and stored until fur-
ther analysis.
2.5. Procedure for determination of heavy
metals
A composite sample of three replicates in the
surface and deep sediments of each station was
separated and completely powdered and ho-
sample was passed through a 63-micron sieve.
-
als are often associated with small grains ,
One gram of dry sediment was weighed and di-
HNO
3
, 5 ml HClO
4
hours. After cooling, the samples were filtered
diluted and then adjusted to 25 cc volume using
-
trifuged at 400 rpm for 6 minutes and stored in
special plastic containers. For validation, Some
of samples digested by microwave digestion
method (MWM) and compared to proposed pro-
cedure. 5 replicate samples and 2 blank samples
were used with the aim of accuracy of analyti-
cal results and eliminating the error caused by
the test process. Also, all plastic and glass con-
tainers for digestion and measurement of heavy
metals were immersed in 10% nitric acid for 24
hours and then washed three times with distilled
water before use. Finally, the concentrations of
measured by the flame atomic absorption spec-
validated by electrothermal atomic absorption
2.6. Potential environmental risk index
-
ly used to evaluate the potential environmen-
tal risk of heavy metal pollution in the coastal
sediments and the sensitivity of the biological
proposed by Hakanson in 1980 for calcu-
lating the potential environmental risk was pro-
posed as follows:
where Cf is the contamination index of heavy
metal, C
s
is heavy metal concentration in the
sample, Cb is the background value of the each
heavy metal (element concentration in shale),
RI is the total potential environmental risk of
is as a toxicity response factor, by showing the
toxicity potential of heavy metals and environ-
mental sensitivity to contamination, indicate
the potential risk of heavy metal contamina-
Ni and Mn are 5, 5, 5 and 1, respectively .
Table 3 shows the environmental risk status
classification of the studied heavy metals. Also
in this study, the average shale presented by
was used
as the background concentration to determine
the amount of sediment contamination to heavy
elements (Table 4).
65
2.7. Statistical analysis
-
tistical software version 22. First, the normal-
ity of the data was evaluated by Kolmogor-
ov-Smirnov test.
the changes in the concentration of heavy
metals at two depths of 0–5 and 5–20 cm, the
mean equality tests of two independent societies
were used. Also, the importance of the relation-
-
ter analysis was used to explain the correlation
pattern between heavy metals, identify potential
sources and group them based on their similar-
statistical tests was considered 5% (95% confi-
dence level).
3. Results and Discussion
3.1. Heavy metal determination in surface and
deep sediments
heavy metals in surface and deep sediments of
10 sampling stations in Kangan and Siraf ports
are presented in Table 5.
mean concentrations of the studied metals in sur-
face and deep sediments were related to Mn and
with the amount of 121.47 44.20 ± and 5.30
7.09 ±
-1
dry weight of surface sediment and
131.59 70.64 ± and 4.88 8.08 ±
-1
dry weight
of deep sediment, respectively. Among the stud-
ied heavy metals in the surface sediments of the
-
cients of 1.33 and 23 had the highest and lowest
and Cu with the variation coefficients of 1.65 and
0.28 had the highest and lowest values, respec-
tively. A variation coefficient of less than 1 and
indicates low variability, while a variation coef-
ficient of greater than 1 indicates high variabil-
ity and non-uniform distribution of the studied
heavy metals in sediment . In this study, only
lead metal in surface and deep sediments had a
variation coefficient of greater than 1. Moreover,
the different techniques for heavy metal deter-
-1
) in surface and deep sediments
of Kangan and Siraf ports coasts was used and
shown in Table 6. Also, the results of comparing
the concentrations of heavy metals such as, Cu,
the coasts of Kangan and Siraf ports showed that
there is no significant difference between their
(Table 7).
Table 3.
Category risk levels DescriptionCategory risk levels Description
Low riskLow risk
Moderate risk Moderate risk
Considerable riskConsiderable risk
High riskHigh risk
--
Table 4. Concentration of metals in average shale (ppm)
MnNiCuMetals
850684520Average
66
Anal. Method Environ. Chem. J. 3 (4) (2020) 60-71
Table 5.
-1
) in surface and deep sediments
of Kangan and Siraf ports coasts
Depth of sampling Descriptive statistics
Heavy metals
Pb Cu Ni Mn
Surface sample
minimum 0 7.55 3.27 70.72
maximum 17.82 16.57 28.37 203.3
Average 5.30 11.59 11.51 121.47
Standard deviation 7.09 2.76 7.07 44.20
1.33 0.23 0.61 0.36
skewness 1.19 0.32 1.53 0.95
kurtosis -0.05 -0.38 3.37 -0.13
Deep sample
minimum 0 8.77 2.37 53.62
maximum 22.25 20.97 28.87 294.6
Average 4.88 12.56 10.81 131.59
Standard deviation 8.08 3.64 7.65 70.64
1.65 0.28 0.70 0.53
skewness 1.71 1.57 1.48 1.44
kurtosis 1.67 2.46 3.06 2.44
Table 6.
-1
)
in surface and deep sediments of Kangan and Siraf ports coasts (n=5, mean SD < 5%)
Surface sample
Techniques
Heavy metals
Pb Cu Ni Mn
F-AAS 5.30 11.59 11.51 121.5
5.41 11.06 12.02 119.9
5.23 10.93 11.42 125.7
Deep sample
F-AAS 4.88 12.56 10.81 131.59
5.12 12.14 11.24 126.82
4.73 12.35 11.03 124.27
Table 7. Results of comparing the concentration of heavy metals in surface
and deep sediments
Metal Test statistics signicance level
0.122 0.904
Cu -0.671 0.511
Ni 0.210 0.836
Mn -0.384 0.705
67
3.2. Correlation analysis and determination of
heavy metals origin
studied metals are presented in Table 8. Accord-
ingly, in sediment samples, there is a positive
and moderate correlation between Cu and Ni as
well as Ni and Mn at the level of 1% and 5%, re-
As the concentration of Ni
increases, the concentrations of Cu and Mn in-
-
logical property, common resources, or similar
behaviors of these elements. Also, all metals in
cluster analysis were classified into two statisti-
cally significant clusters based on the similarity
first subgroup consisted of Cu and Ni with sim-
ilar geological property which had positive and
significant correlation, and the second group
included Mn, which may be derived from both
-
greater distance compared to the first cluster.
cluster analysis and the results were presented
as a dendrogram chart (Fig. 2)
cluster analysis almost confirmed the results of
correlation analysis.
Table 8.
MnNiCuMetal
1
10.104Cu
10.583
**
-0.332Ni
10.444
*
0.175-0.263Mn
***
Fig. 2. Results of heavy metal cluster analysis in coastal sediments
68
Anal. Method Environ. Chem. J. 3 (4) (2020) 60-71
3.3. Environmental risk evaluation
heavy metals in the surface and deep sediments of
the studied stations were less than 150, which indi-
cated the low environmental risk of heavy metals
in Kangan and Siraf coastal areas. Also, the indi-
metals was less than 40 and showed the descend-
sediments.
3.4. Discussion
Nowadays one of the most important global envi-
ronmental problems is pollution caused by heavy
metals. High concentrations of metals along with
high durability, inherent toxicity and consequently
accumulation in the food chain play an important
metals in the collected samples of surface and deep
-
gan and Siraf ports.
Heavy metals are affected by oil pollution and re-
as the common pollution in the study area. In this
study, the highest concentrations of heavy metals in
surface and deep sediments include Mn, Cu, Ni and
-
ing the study by Hosseini and Habibi et al ,
the concentration of Mn, Ni and Cu in the region is
concentration of heavy metals in the coasts of Asa-
concentration of industries in this region, the con-
centration of pollutants is much higher than other
-
tion of heavy metals in industrial and commercial
areas compared to non-industrial areas showed that
human activities strongly affect the concentration
and distribution of heavy metals in the environ-
ment. Industrial and agricultural wastewater, sol-
id and liquid wastes and atmospheric emissions
increase the concentration of metals in sediments
of the area. Atmospheric sediments can affect large
areas according to population distribution and in-
dustrial activities . Also, erosion and washing
possible sources of sediment pollution and accu-
mulation of heavy metals on the coast
results of comparing the concentrations of heavy
metals in the two coastal areas of Kangan and Siraf
showed the existence of concentration differences
between them, which can be due to various reasons
such as the number and type of pollutants in the en-
vironment, the distance from the source of contam-
ination to the sampling site, sediment texture and
mineralogical compositions, physical and chemical
properties of sediment such as pH and temperature,
amount of sediment organic matter and also the ef-
fect of environmental factors on metal deposition
stations located in Kangan and Siraf ports can be
attributed to various agricultural activities such as
-
ers and soil conditioners, drip irrigation pipes, re-
pair of agricultural equipments and the use of pes-
ticides. In addition, the existence of petrochemical
-
ents to the coast, as well as high human activities
and their discharge of sewage and waste can be
considered as the effective factors in the increase
of heavy metal concentrations on the coastal areas.
Furthermore, the heavy metal pollution in the re-
gion could be due to the use of small rivers water
to irrigate agricultural lands. Rivers water may be
contaminated by discharge of municipal and in-
dustrial wastewater from the upstream wastewa-
ter treatment plants. Irrigation with contaminated
in coastal sediments . In this study, stations K
7
and K
2
showed the highest concentrations of heavy
metals in surface and deep sediments, respectively.
Station K
7
is located near an area with high agri-
cultural activities and Station K
2
is adjacent to the
Wang et al also showed that the samples collect-
ed from agricultural soil contained large amounts
69
Ni and Mn in the station K
7
sediments indicated
their common sources and similar behavior . In
addition, the results of multivariate statistical an-
to the geological origin and human activities relat-
ed to oil products in the region
sources of nickel include minerals such as clay,
sandstone and basalt
et al was showed that the origin of Ni in the re-
gion is probably due to dyes used in machinery and
ships industry . In addition, the concentration of
Mn in sediment may increase due to human activ-
ities such as discharge of municipal and industrial
-
sumption of diesel fuel in motor boats. Also, Mn
is easily removed from igneous and metamorphic
rocks due to weathering of rocks and in interaction
with surface and groundwater, and is released into
aquatic environments . Cu is also widely used
due to its special physical properties and usually ac-
cumulates in soils and sediments following human
activities . In this study, the highest concentra-
with agricultural activities. As a result, the presence
of Cu in the region can be due to the discharge of
municipal sewage and agricultural pesticides on
the coastal area and also the release of paint used in
conveyors, ships and vessels in the water environ-
ment which is in line with the study by Haghshenas
et al
so human activities increase the concentration of
comes from the oil industry, lead-containing paints
from dyes is related to the proximity of the struc-
tures to the coastal areas and their age. While the
the emission of polluted gases by vehicles depends
. Among the studied
stations, stations S
2
and K
5
concentrations in surface and deep sediments, re-
from the ships’ body, proximity to roads and road
industrial wastewater discharge . In general,
factors such as high temperature and humidity on
-
rosion process of metal smithereens, which mostly
include Cu and Ni alloys. Also, the oil-richness of
the region, the existence of activities related to the
oil industry and the transport of metal-containing
sediment particles by rivers and surface runoff,
cause the discharge of metals in the environment
and their accumulation in the sediments of the re-
gion .
4. Conclusions
strategic region that contributes to the economic
growth of the country due to its beautiful scenery
and rich resources of oil and gas. However, there
is a possibility of contamination of these beaches
with heavy metals due to various land and sea ac-
tivities, mismanagement of solid wastes and dis-
charge of various industrial and municipal waste-
metals are pervasive in surface and deep sediments
of all studied stations and the distance from the
source of pollution, environmental conditions and
sediment characteristics have caused differences in
the frequency and concentration of these pollutants
in different stations.
deep sediments were studied and determined by
F-AAS, which almost all stations had the highest
concentration of Mn and the lowest concentration
correlation between Cu and Ni as well as Ni and
-
es, so does the concentration of Cu and Mn. Also,
All samples were validated by microwave diges-
70
Anal. Method Environ. Chem. J. 3 (4) (2020) 60-71
ecological risk assessment index to determine the
environmental risk of heavy metals showed that
the sediment contamination status of these metals
was not in a dangerous and critical state. However,
regular management and preventive measures are
necessary to prevent the increase of heavy metal
pollutants in the environment.
5. Acknowledgments
-
viewers for their valuable comments.
6. References
-
er, Levels and ecological risk assessment of
Bull., 136 (2018) 322-333.
M.J. Mohammadi, M. Keshtkar, M. Khor-
plastic debris and association of metals with
microplastics in coastline sediment along the
658.
-
spatial distribution, and ecological risk of
heavy metals in coastal sediments of northern
-
ron., 653 (2019) 783-791.
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US department of health and human services,
national institute for occupational safety and
health (NIOSH). Adult blood lead epidemiol-
www.cdc.gov/niosh/topics/ables/description.
html
-
butions of heavy metals and their potential
toxicity levels in various beach sediments
from high-backgroundradiation area, Kerala,
-
-
centration in pontogammarus maeoticus and
-
Animal Res., 30 (2017).
Metals and their ecological impact on beach
sediments near the marine protected sites of
Sodwana Bay and St. Lucia, South Africa,
-
347-359.
S. Ganji, Distribution and ecological risk
assessment of heavy metals in surface sedi-
ments along southeast coast of the Caspian
Q. Li, Heavy metal contamination assess-
ment of surface sediments of the Subei Shoal,
China: Spatial distribution, source apportion-
ment and ecological risk, Chemosphere, 223
(2019) 211-222.
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-
Assessment of heavy metal contamination
Nadu affected by different pollution sources,
71
aquatic pollution control, a sedimentological
approach, Water Res., 14 (1980) 975–1001.
-
chemical distribution, fractionation and con-
tamination assessment of heavy metals in
-
411.
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tion of the elements in some major units of
(1961) 175-192.
-
in tissues of two sea cucumbers, Holothuria
leucospilota and Holothuria scabra in the
Lin, G. Hu, Heavy metals distribution and en-
vironmental quality assessment for sediments
-
483-488.
-
-
28 (2014) 441-449.
Determining the level of impurity of coastal
sediments in Bushehr province in relation to
-
bution, ecological and health risk assessment
-
ments and coastal seawaters of fringing coral
185 (2017) 1090-1111.
Occurrence and distribution of microplastics
-
M.R. Hemami, Bioaccumulation of heavy
metals (Hg, Cd and Ni) by sentinel crab
(Macrophthalmus depressus) from sediments
-
viron. Saf., 191 (2020) 109986.
trace metals contamination in the coastal sed-
Bardkashki, Determination and ecologi-
cal risk assessment of heavy metals (Cd,
-
-
risk assessment of trace metals in the surface
Oman: evidence from subtropical estuaries
of the Iranian coastal waters, Chemosphere,
191 (2018) 485-493.
Anal. Method Environ. Chem. J. 3 (4) (2020) 72-84
Research Article, Issue 4
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Separation of aniline from water and wastewater samples
based on
activated carbon nanoparticles
and dispersive
solid phase extraction procedure
Saeed Fakhraie
a,*
, Morteza Mehdipour Rabouri
b
and Ahmad Salarifar
c
a
Chemistry Department, Yasouj University, P.O. Box 74831-75918, Yasouj, Iran.
b
Occupational Health Engineering Department, , Kerman University of Medical Sciences, Kerman, Iran
c
Environmental Engineering, Faculty of Natural Resources, Islamic Azad University, Bandar Abbas Branch, Iran
ABSTRACT
in environment. Aniline has a toxic effect in the human body and
environment and so, must be determined by novel techniques. In this
study, the
activated carbon with microwave heating methods
and compared to the
activated carbon
(AC). For this purpose,
AC added to 100 mL of water samples at pH=8. After sonication
electron acceptor
was
chemically adsorbed on
as
electron donors
……C
6
H
5
-NH
2
) and then,
the adsorbent was collected by hydrophobic ionic liquid phase in
bottom of conical centrifuging tube. Finally, the aniline was released
concentration of aniline determined by gas chromatography–
from 2.0 to 4000 µg L
-1
0.6 µg L
-1
µg L
-1
method was validated by spiking of real samples and analysis with
gas chromatography mass detector (GC-MS).
Keywords:
Aniline,
Activated carbon nanoparticles,
Ionic liquid,
Dispersive solid phase extraction
procedure,
gas chromatography–mass
spectrometry
ARTICLE INFO:
Received 10 Aug 2020
Revised form 4 Oct 2020
Accepted 22 Nov 2020
Available online 29 Dec 2020
*Corresponding Author: Saeed Fakhraie
saeedfakhraie@yahoo.com
https://doi.org/10.24200/amecj.v3.i04.126
------------------------
1. Introduction
Aromatic amines such as aniline compounds
are employed as the chemical in industries
(polyurethane foams) and pharmaceutical product.
or iron) or dihydrogen in polar solvents. Aniline
is an aromatic hydrocarbon and discharge into the
which thereby cause to water contamination .
Aniline (C
6
H
5-
NH
2
2
bond can be reacted to other chemicals with sulfur
and carboxyl groups and removed from waters
.
diphenyl diisocyanate (MDI) which was used in
polyurethanes as foams in refrigerator insulation.
Aniline use in different industries such as paint,
polymers, pesticides, herbicides, resins, chemicals,
antioxidants, pharmaceuticals, rubber, plastics,
73
explosives and solvents in perfumes . It should
also be noted that the WHO reported the threshold
-1
showed, water containing aniline at an average of
6-60 µg L
-1
is not greater than a one-in-a hundred
thousand increased chance of developing cancer.
Aniline is toxic in humans and cause to mutagenic
or carcinogenic effect in the cells of body and DNA
. Aniline cause to myelotoxicity, toxicity of
lymphoid organs and hematopoietic tissues in
human and faunae . Aniline compounds belong
to the blacklist of contaminants material in many
countries. Aniline create the reactive oxygen species
(ROS) and cause to rise lipid hydroperoxide stages,
damage of mitochondrial membrane, damage DNA
and lead to variations in hepatocyte feasibility and
apoptosis . Also, the acute exposure aniline has
toxic reaction in the spleen or liver and cause to
with chronic exposure
carcinogenicity of aniline was reported by NIOSH
and OSHA .
caused to convert to 4-hydroxyaniline and the
formation of aniline compound with hemoglobin
(Hb). In erythrocytes(RB), this is associated with
the release of iron (Fe) and the accumulation of
methemoglobin (MHb) and the development of
on prolonged administration.
aniline as a group 2B carcinogenic compound owed
to its mutagenic and carcinogenic possible and
the concentration of aniline must be evaluated
in water samples. So the removal of aniline
compounds from wastewater is mainly important
analytical techniques include, gas chromatography
,
injection and high performance liquid
chromatography were used for the
determination of aniline and derivatives in real
the biological degradation, the catalytic oxidation
and the electrochemical procedure was used for
eliminating aniline compounds from waters .
Due to toxicity of aniline and its derivatives, the
aniline value must directly evaluate in water sources.
As low concentration of aniline compounds in
water samples, the pretreatment/preconcentration
GC and liquid chromatography-tandem mass
spectrometry . Conventional techniques such
as, adsorption, extraction, the chemical oxidation,
the the electrochemical, the
for anilines separation and determination in water
method for the removal of aromatic pollutants from
wastewaters by peroxidases . On the other
hands, adsorbents such as graphene, graphene
oxide, carbon nanotubes, MOF and silica with
different physical and chemical properties were
used for extraction/adsorption anilines from waters.
were used for extraction aniline from waters by
dispersive ionic liquid solid phase extraction
COO…. NH-C
6
H
5
and determined by GC-FID.
2. Experimental
2.1. Apparatus
detector (GC-FID) and mass detector (GC-MS)
model of GC based on different detectors and
equipped with a split injector was used for aniline
analysis. A Hamilton syringe was used for the
up to 185-200
o
min
-1
for H
2
74
injected into a GC injector with high temperature
based on valves to the GC column (0.32 mm ×
tuned between 35-100 psi for hydrogen with FID
aniline results which were adsorbed on MHM-
presented in Table 1.
2.2. Reagents
were provided by
China. According to our previous study
ash content (7%), water ratio (3%), high
energy dispersive spectrometer instrument
(
C: 42.16%). Aniline is an aromatic amine that
may be used as a reactant in the synthesis of
organic intermediates such as pyridine amine,
Aniline prepared (CAS N: 62-53-3) from Sigma
Aldrich. Hydrophobic ionic liquid 1-Butyl-1-
imide (C
11
H
20
F
6
N
2
O
4
S
2
, 223437-11-4) with density
of 1.4 g cm
-3
and low solubility in water was used
for collecting of nanoparticles from liquid phase.
Acetone, nitric acid and HCl were purchased from
Merck, Germany. Ultrapure water was obtained
buffer (H
2
4
4
) and ammonium buffer (NH
3
/
NH
4
Cl) prepared from Sigma an used for adjusting
pH between 6.0–8.2 and 8-9, respectively.
2.3. Synthesis of adsorbent
2.3.1.Carbonization
heats biomass feedstock in a kiln (pyrolysis) at
and carbon-enriched).
Firstly, 20 g of raw powders prepared and
placed in the porcelain crucible, then heated
hours. By decreasing temperature up to
25
o
C, the product is ready for weight .
2.3.2.MHM-ACNPs Synthesis
heating method caused to create
the MHM-
.
First, the
Table 1. Gas chromatography conditions (Agilent, 7890A)
ValuesParameters
2:1Split ratio
Column
Detector FID
H
2
@ 1.5 mL min
-1
Carrier Gas
N
2
@ 30 mL min
-1
Gas Makeup
18.1 (min)N,N-Dimetnylaniline
10.9 (min)Aniline
28 (mL min
-1
)Flow Rate N
2
60(mL min
-1
)Flow Rate detector H
2
450(mL min
-1
)Flow Rate air
Anal. Method Environ. Chem. J. 3 (4) (2020) 72-84
75
-
1
down to room temperature under N
2
(0.5 Lmin
-1
). In the microwave heating
method, the
were achieved by
microwave furnace at a frequency of 2.45
placed in
the microwave furnace (800 W)
and heated for 12 min
cooled up to 25
o
C under N
2
-
1
were washed with 10%
HCl and then
washed with DW up to pH=7.
2.4. Extraction procedure for aniline
water samples at pH=8. After extraction, the
concentration of aniline determined by GC-FID.
acetone (1 mL) and 1-butyl-1-methylpyrrolidinium
injected to water and standard solution of aniline
(2.0 µg L
and 950 µg L
). After sonication for
electron
acceptor
was chemically adsorbed on
carboxylic
as
electron donors
……C
6
H
5
-NH
2
).
from the liquid phase in the bottom of the conical
upper of the liquid sample was removed and then,
in acidic pH (HNO
3
, 0.3 mol L
-1
). After shaking
and centrifuging, the remained solution diluted
up to 0.5 mL with DW and determined by GC-
FID (Fig. 1)
experimental run without any aniline for ten times.
procedure (2.0- 950 µg L
) and GC-FID method
(0.4- 800 mg L
(m
1
/m
2
means of a GC-
a FID detector. Aniline (mol) were calculated by
%Recovery = Final aniline amount (mol)/ Initial
aniline amount (mol) × 100 (2)
3. Results and Discussion
Fig. 1.
76
with high surface area (2792 m
2
g
-1
) and
extracted the aniline (
NH
2
-C
6
H
5
) in water
samples as compared to ACs
important parameters on aniline extraction
such as, pH, amount of ionic liquid, sample
volume, amount of sorbent, amount of IL,
shaking time were studied.
3.1. FTIR of MHM-ACNPs
is illustrated
in Figure 2
-1
was
attributed to the stretching vibration of hydroxyl.
-1
bands were respectively
assigned to asymmetric and symmetric C–H
band at 1710 cm
-1
mode of carboxylic groups, while the peak at 1058
cm
-1
peak at 1613 is characteristic of stretching vibration
seen between 850 and 500 cm
-1
, which are ascribed
to C-H and CH=CH
2
vibrations in aromatic rings.
3.2. SEM and TEM of MHM-ACNPs
study of prepared
(Fig. 3).
Figure 3a and b
sample
displayed small broken pieces of particles with
and average pore diameter). From Figure 3b,
appeared to have many different
been destroyed and a dense porosity was formed
through KOH activation. In order to observe the
structure of
anoadsorbents, HR-
500100015002000
2500
300035004000
% Transmitance
Wavenumber (cm
-1
)
O-H
C-H
C=O
C=C
C-O
Fig. 2.
spectrum
Anal. Method Environ. Chem. J. 3 (4) (2020) 72-84
77
(Fig. 3c) clearly shows the graphene-like structure
with a 2D morphology, and the image with 50 nm
scale (Fig. 3d)
graphitic layers and porous structure.
3.3. Optimizations of parameters for extraction
aniline
nanocomposite was used for extraction of aniline
(NH
2
-C
6
H
5
main effectiveness parameters such as, pH, amount
sonication
time, volume of samples, adsorption capacity of
sorbent were evaluated and studied.
electron acceptor
was adsorbed
on
carboxylic groups of sorbent
as
electron
donors
(R-COO
……C
6
H
5
). After extraction,
the sorbent/aniline was collected by1-butyl-1-
imide as a hydrophobic ionic liquid phase in bottom
of conical centrifuging tube.
3.3.1.
pH effect on aniline extraction
Fig.3. (c)
by 2D morphology (d)
with intermittent graphitic layers and porous structure
Fig. 3. (a)
(b)
78
extraction in water samples and must be studied.
different buffer solution and the recovery of
aniline extraction in water samples was evaluated
in presence of aniline concentration between
µg L
-1
on results, the extraction of aniline was reduced
at acidic pH (pH<6) and pH of 7-9 had more
extraction for aniline in waters (Fig. 4). So, in this
study, the pH of 8.0 was
for aniline extraction in waters.
3.3.2.The effect of
MHM-ACNPs adsorbent
on aniline extraction
By proposed method, the amounts of on MHM-
adsorbent
for 100 mL of water and
and AC was
in pH=8. So, the amount of 30 mg of
adsorbent
was selected for aniline
extraction in water samples (Fig. 5).
3.3.3.The effect of
sample volume
on aniline
extraction
extraction in water samples. For this proposed, the
effect of sample volume for extraction of aniline
in waters was evaluated. By procedure, the various
sample volumes between 20-150 mL was used for
-1
of
selected for further studies (Fig. 6).
3.3.4.The adsorption capacity
the nanoparticles of adsorbent were dispersed
in water samples and used for aniline extraction
experimental results showed, the aniline was
for 19 cycles of extraction at pH=8.0. So, the MHM-
absorption capacities of adsorbents depended on
the structure, surface area (SA) and nanoparticle
Fig. 4.
and AC adsorbents from water samples
Anal. Method Environ. Chem. J. 3 (4) (2020) 72-84
79
and AC
nanoparticles
was added to 100 mL of
water samples with 20 mg L
-1
(ppm) of aniline
concentration at pH of 8.0. After 30 min sonication,
in solutions. Finally, the concentrations of aniline
directly determined in remain solution by GC-FID.
AC structure for aniline were achieved 155.8 mg
g
-1
and 77.2 mg g
-1
, respectively in water samples.
3.3.5.Aniline validation in real samples
determination and extraction aniline in water and
proposed procedure and validated by spiking of
real samples (Table 2)
were obtained by spiking of water samples with a
standard aniline at pH=8.0.
Fig. 5. and AC adsorbents
on aniline extraction
Fig. 6.
adsorbents
80
was satisfactory results for aniline extraction
and determination in in water and wastewater
samples at pH of 8.0. Moreover, the GC-MS were
used for validating of methodology based on
procedure (Table 3). Also, the aniline extraction
and technology which was shown in Table 4.
3.3.6. Discussion
Recently, the aniline was removed/extracted from
different matrixes by various technologies by
and techniques for extraction aniline from
water and wastewater samples and the various
analytical parameters such as, LOD, LOQ, linear
range, RSD% and absorption capacities reported
which was shown in Table 4. Kakavandi et al
were used the Fe
3
O
4
-activated carbon magnetic
Table 2.
samples by spiking of standard solutions
Sample Added
(μg L
-1
)
*Found
(μg L
−1
)
Recovery (%)
----- 4.24 ± 0.22 -----
5 9.31 ± 0.24 101.4
Drinking water ----- ND -----
10 9.82 ± 0.46 98.2
Well water ----- 19.54 ± 0.95 -----
20 38.98 ± 1.84 97.2
wastewater ----- 335.92 ± 15.11 -----
300 628.33 ± 27.65 97.5
Wastewater ----- 188.60 ± 8.75 -----
200 379.70 ± 16.40 95.6
*x_ n
Table 3.
samples by GC-MS
Sample
Added
(μg L
-1
)
GC-MS
(μg L
−1
)
* D-IL-SPE/GC-FID
(μg L
−1
)
Recovery (%)
Water A ----- 11.35 ± 0.28 10.96 ± 0.53 96.6
10 ----- 20.78 ± 0.24 98.2
Water B ----- 53.14 ± 0.57 53.78 ± 2.44 101.2
50 ----- 102.66 ± 4.82 97.8
Water C ----- 98.53 ± 1.67 101.03 ± 5.12 102.5
100 ----- 199.87 ± 9.34 98.8
Water D ----- 202.38 ± 4.12 195.82 ± 10.13 96.8
200 ----- 400.08 ± 18.52 102.1
*x_ n
Anal. Method Environ. Chem. J. 3 (4) (2020) 72-84
81
. Also, the results were
showed by two kinetic models for adsorption of
300 mg L
-1
and between 21.1-99%, respectively.
Rahdar et al were presented a novel magnetic
Fe
2
O
3
@SiO
2
for removal aniline from waters by an
electrochemical method. Due to the special
such as, vibrating-sample magnetometry
caused to efficient extraction of aniline from
the water samples.
50 mg of Fe@SiNp can be removed aniline in
waters with absorption capacity of 126.6 mg
g
-1
at pH 6 (50
o
C) which was lower than the
proposed
of aniline by Fe@SiNp is fast and exothermic
which was shown by the kinetic model (r
2
= 1)
and the Freundlich isotherm model (r
2
= 0.9986)
for extraction of aniline in water samples.
Raman spectroscopy (RS), the differential
scanning calorimetry (DSC), and field-emission
was achieved around 99% for aniline in waters
. Based on our study, the were
used for fast, simple and efficient extraction
aniline from waters by dispersive ionic liquid
aniline adsorbed on nanostructure (
-COO…. C
6
H
5
) with high absorption capacity,
the recovery and the extraction as compared to
other methods. After back-extraction of aniline,
the concentration of aniline is determined by
working range was obtained from 2.0 to 4000 µg
L
-1
(RSD% < 1.8) which was higher than other
published methodsthe LOD,
methods.
Table4. Comparison of proposed procedure with other published methods
Adsorbent Matrix Method Linear range Instrument Recovery
(%)
References
C8-column Water 0.05- 2 µg L
-1
LC- MS/MS 99-102%
Water Adsorbent 50-300 mg L
-1
21.1-99%
Soybean peroxidase Wastewater ----- 95%
-------- Water NIAA 50–1000 µg L
-1
93-104%
Activated carbon (AC) Wastewater 20-600 mg L
-1
89–94%
MFH nanocomposites Wastewater 50-200 mg L
-1
XRD 95.1%
0.03–1.4µg L
-1
21–110%
Water Adsorption 2.0-950 µg L
-1
GC-FID/ 95-102%
NIAA: Non-ionic or anionic analytes
82
4. Conclusions
In this study, a robust procedure based on MHM-
adsorbent was used for the aniline
MHM-
separated/collected
from water samples in bottom of conical tube
by hydrophobic 1-butyl-1-methylpyrrolidinium
preconcentration, and the prefect sample preparation
was
recovery between 95-102% for aniline extraction
favorite reusability, low LOD and RSD% with
on
FID procedure.
5. Acknowledgements
Iran
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