Anal. Methods Environ. Chem. J. 4 (3) (2021) 5-20
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Adsorption and determination of Lead in water and human
urine samples based on Zn
2
(BDC)
2
(DABCO) MOF as
polycaprolactone nanocomposite by suspension micro solid
phase extraction coupled to UV–Vis spectroscopy
Negar Motakef Kazemi
a,*
and Masomeh Odar
b
a
Department of Medical Nanotechnology, Faculty of Advanced Sciences and Technology, Tehran Medical Sciences,
Islamic Azad University, Tehran, Iran.
b
Department of Nanochemistry, Faculty of Pharmaceutical Chemistry, Tehran Medical Sciences,
Islamic Azad University, Tehran, Iran
ABSTRACT
Today, the safety of water resource is the most important challenges
which was reported by health and environment organizations.
Water pollution can be created by hazardous contaminants of
environmental pollutions. Lead as a heavy metal has carcinogenic
effects in humans. Metal organic framework (MOF) is a highly
porous material with different application. The Zn
2
(BDC)
2
(DABCO)
is a good candidate of MOF based on zinc metal (Zn-MOF) with
potential adsorption/extraction. In this work, Zn
2
(BDC)
2
(DABCO)
MOF as polycaprolactone (PCL) nanocomposite were applied for
lead adsorption/extraction from 50 mL of aqueous solution by ultra-
assisted dispersive suspension-micro-solid phase extraction procedure
(USA-S- µ-SPE) at pH=8. The samples were characterized by the
FTIR, the XRD analysis, the FE-SEM and the BET surface area.
The effect of parameters was investigated on lead absorption before
determined by UV–Vis spectroscopy. The linear range, the detection
limit (LOD) and enrichment factor of adsorbent were obtained 0.05-1
mg L
-1
-1
and 48.7, respectively (r = 0.9992, RSD%=3.65).
The absorption capacity of Zn
2
(BDC)
2
(DABCO) MOF for 50 mg L
-1
of standard lead solution were obtained 133.8 mg g
-1
for 0.25 g of
adsorbent. The results indicate that this nanocomposite can have a
good potential to develop different adsorbents.
Keywords:
Lead,
Metal organic framework,
Polycaprolactone,
Nanocomposite,
Adsorption,
Suspension-micro-solid phase
extraction procedure
ARTICLE INFO:
Received 25 May 2021
Revised form 23 Jul 2021
Accepted 9 Aug 2021
Available online 28 Sep 2021
*Corresponding Author: Negar Motakef Kazemi
Email: motakef@iaups.ac.ir
https://doi.org/10.24200/amecj.v4.i03.145
------------------------
1. Introduction
Heavy metals are considered one of the major
pollutants with harmful effects on the environment
and living organisms [1]. Lead is one of heavy metals
with many industry applications. Lead element is a
very strong poison and major environmental health
problem. This non-biodegradable pollutant can be
caused detrimental effects on human health [2]. The
lead as a hazardous material that needed to protect
the health of workers, children and women of
childbearing age. Threshold limit value (TLV) is the
weighted average concentration of the risk factor
in the atmosphere [1-3]. According to the results
of workers in battery storage plants, TLV (working
day of eight hours) was obtained about 0.1 mg m
-3
and normal lead concentration in urine of workers
-1
. The US Environmental
6
Anal. Methods Environ. Chem. J. 4 (3) (2021) 5-20
-1
as
a reference value in bottle and drinking water [3]. The
lead effects on human health and causes the different
diseases in humans such as, CNS defect, the nerve
system damage, the renal/liver/bone dysfunction. The
organic lead compound such as Triethyl and methyl
lead with the Pb(II) as inorganic lead
are toxic for
the humans [3]. Lead emitted to environment with
(C
2
H
5
)
3
/(CH
3
)
3
-Pb and Pb(II) forms and can be
dispersed by oil/gasoline additives [4]. The organic
lead is used in for industries, which can simply enter
to human body by the skin and respiratory system.
The organic lead with good hydrophobicity in organic
solvent and foods has toxic effect in humans [5]. So,
determination lead in water and human liquid samples
(urine) is very important. Various methods have been
developed to removal of each toxic heavy metal from
water [6,7] such as the chemical precipitation [8],
the ion exchange [9], the reverse osmosis [10], and
the adsorbent process [11]. Recently, lead adsorbent
from aqueous solution is a real challenge due to use
widespread all over the world [12]. The adsorption
for lead removal from wastewater [13]. The various
adsorbents included, the graphene/graphene oxide
[14] [15], the
carbon nanotubes (CNTs) [16], the magnetic doped
with carbon quantum dots(MDCQDs) [17], and the
silica nanostructure [18] were widely used for lead
extraction in water samples. Metal organic frameworks
(MOFs) are a new class of porous coordination
polymers with a variety of applications [19, 20]. They
are formed of organic ligands as linkers and metal
ions or clusters as metal centers [21, 22]. Recently,
the MOFs have attracted a great attention because
of unique properties [23, 24]. Zn
2
(BDC)
2
(DABCO)
MOF is metal organic framework based on
zinc metal (Zn-MOF) by connection of Zn
4
O
units and 1,4-benzenedicarboxylate (BDC) and
1,4-diazabicyclo [2.2.2] octane (DABCO) ligands
via self-assembly such as solution [25], solvothermal
[26] and other methods. The common adsorbent
compounds have expanded based on MOFs [27].
Zn
2
(BDC)
2
(DABCO) MOF was loaded with various
materials such as mercury [28], the gentamicin [29],
the Pd(II) [30], the methane [31], the azobenzene [32]
and etc.
Easy separation of sorbent from the water is
metals during treatment. Therefore, the adsorbents
were developed based on magnetic [33-36] and
polymer [33, 37] materials. Polycaprolactone is one
of the most common polymers for the removal of
heavy metals from aqueous solutions as hazardous,
carcinogenic, and toxic pollutants. According to
for lead adsorption [38]. Also in another report,
cyclodextrin-polycaprolactone titanium dioxide
nanocomposites were used as a adsorbent for the
removal of lead in aqueous waste samples [39]. The
different techniques included, the graphite furnace
coupled with atomic absorption spectrometry(GF-
AAS) [40], the anodic stripping voltammetry (ASV)
[41]
(F-AAS) [42], the inductively coupled plasma
atomic emission spectrometry (ICP- AES) [43] and
the UV-Vis were used for lead determination in water
samples. In present study, Zn
2
(BDC)
2
(DABCO)
MOF/PCL nanocomposites were prepared by a
simple method and lead absorption was investigated
by MOF and its nanocomposites from aqueous
solution at optimized pH.
2. Experimental
2.1. Reagents and Materials
All reagents with high purity and analytical
grade were purchased from Merck (Darmstadt,
Germany). Ultra-pure water was used for the
preparation of all reagent’s solutions. Zinc acetate
ehydrate (Zn(Oac)
2
.2H
2
O, CAS N:5970-45-6,
Sigma, Germany), 1,4 benzenedicarboxylic acid
(CAS N: 652-36-8, Sigma), 1,4-diazabicyclo [2.
2.2] octane (CAS N: 280-57-9, Sigma), N,N-
dimethylformamide anhydrous (DMF, CAS N: 68-
12-2) were used for synthesis of MOF. The lead
502-44-3, Sigma, 1400 g mol-1, molecular weight)
were applied for preparation of lead and polymer
solution respectively.
7
Lead extraction in human sample by Zn2(BDC)2(DABCO) MOF Negar Motakef Kazemi et al
2.2. Sample preparations
For sampling, all glass tubes were washed with
a 2.0 mol L
-1
HNO
3
solution for at least 12 h and
rinsed 8 times with DW. The lead concentrations
in humans have low concentration (ppb) in
urine/water and even minor contamination for
sampling and determination caused to effect on the
accuracy of the results. By procedure, 50 mL of
the urine samples were prepared from workers of
batteries factories in Iran (Men, 25-55 age), based
on ethical low. Clean and sterilized bottles were
prepared for urine or water sampling. The water
samples were prepared based on ASTM sampling
and storage in 2% HNO
3
.
2.3. MOF Synthesis
For preparation of Zn
2
(BDC)
2
(DABCO) MOF, Zn
(OAc)
2
.2H
2
O (0.132 g, 2.0 mmol) to production of
Zn
2+
ions as a connector, BDC (0.1 g, 2.0 mmol)
as a chelating ligand, and DABCO (0.035 g, 1.0
mmol) as a bridging ligand were added to 25 ml
DMF as a solvent [28]. The reactants were sealed
reaction mixture was cooled to room temperature,
DMF to remove any metal and ligand remained,
and dried in a vacuum. DMF was removed from
5 h. Based on lead absorption, polycaprolactone
nanocomposites cannot be prepared by solution
up with solvent and there is not any residual
porosity for lead absorption. In this work, PCL
nanocomposites were prepared by press method
with different percentages of
First, PCL polymer was dissolved in chloroform
was transferred to the plate and allowed to dry.
10 minutes. Finally, the certain amount of MOF
powder was uniformly transferred to a cold press
lead absorption, PCL nanocomposites with 5 and 10
percentage of MOF were shown better results and it
was not possible to form a uniform nanocomposite
with a higher percentage of MOF. Finally, the lead
absorption was investigated in different values of
lead concentrations, pH and temperature solution
by MOF and its nanocomposite at different
times. Figure 1 shows general procedure of
Zn
2
(BDC)
2
(DABCO) MOF synthesis and lead
adsorption by MOF.
Fig. 1. General procedure for Zn
2
(BDC)
2
(DABCO) MOF synthesis and lead adsorption by MOF.
8
2.4. Characterization
FTIR spectra were recorded on a Shimadzuir 460
spectrometer in a KBr matrix in the range of 400–
4000 cm
. The crystalline structure of sample was
X-ray radiation with a voltage of 40 kV and a current
of 30 mA by X’pert pro diffractometer (X’ Pert Pro
model, Panalytical, Peru). Field emission scanning
electron microscope was employed to observe
morphology and size (Sigma VP model, ZEISS,
Germany). The surface area was determined using
nitrogen gas sorption by MOF samples at 298 K and
0.88 atmosphere pressure (BElSORP Mini model,
Microtrac Bel Corp, Japan). Lead absorption was
evaluated by UV–Vis spectroscopy (GENESYS 30
2.5. Extraction/Adsorption Procedure
By the USA-S- µ-SPE method, 50 mL of urine
and water samples were used for extraction and
determination lead ions by Zn
2
(BDC)
2
(DABCO)
MOF adsorbent. 0.25 g of Zn
2
(BDC)
2
(DABCO)
MOF added to urine/water or standard solution
(0.05-1 mg L
-1
) at pH=8. After sonication for 5.5
min, the Pb (II) ions were extracted/chemically
adsorbed with the N group of the DABCO as a
dative covalent bond in the optimized pH (Pb
2+
N---MOF). After centrifuging, the lead adsorbed
on Zn
2
(BDC)
2
(DABCO) MOF was separated from
liquid phase in the bottom of the centrifuging tube
(50 mL, 5.0 min; 3500 rpm). The liquid phase was
removed and the lead ions back-extracted from the
Zn
2
(BDC)
2
(DABCO) MOF in acidic pH (HNO
3
,
0.2M, 0.5 mL). The remained solution determined
by UV-Vis after diluted with 0.5 mL of DW (Fig.
2). The calibration curve for lead in the standards
solutions was prepared based on a LLOQ and
ULOQ range with (0.05-1 mg L
-1
) and without a
preconcentration procedure (2- 50 mg L
-1
) and
slop of the two calibration curves(m1/m2)..
3. Results and discussions
3.1. FTIR spectra for MOF
The FTIR absorption spectra of the samples were
recorded in the range of 400–4000 cm
-1
with KBr
pellets. FTIR spectra of MOF were presented before
and after lead absorption (Fig. 3). The C–H aromatic
bands are shown at 3423 cm
-1
. The IR bands of N–H
and O–H stretching vibrations are characteristic at
3300 cm
-1
. The aliphatic C–H asymmetric stretching
is assigned at 2958 cm
-1
. The O–H….O valance
stretching vibration band is reported at 2600 cm
-
1
. The high intensity peak of C=O stretching is
assigned at 1635 cm
-1
for Zn
2
(BDC)
2
(DABCO)
MOF. The bands of aromatic C=C stretching are
shown at 1593 cm
-1
. The high intensity peak of C=O
-1
. The peaks
of obtained results has similar to the previous report
[20, 25, 26]. The bands between 800 and 500 cm
are ascribed to Pb(II) adsorptions that according to
the previous reports [44].
Anal. Methods Environ. Chem. J. 4 (3) (2021) 5-20
Fig. 2. Extraction/Adsorption procedure based on Zn
2
(BDC)
2
(DABCO) MOF adsorbent for lead analysis
9
3.2. XRD analysis
The XRD
structure (Fig. 4). The XRD pattern of MOF is
similar to a previously reported pattern [25, 28]
and its crystalline structure is preserved after the
absorption based on the previous report [27].
The XRD of PCL was approved the crystalline
structure according to the previous report with
two characteristic peaks [45]. The high percentage
of polymer in the nanocomposite was caused no
observation of MOF characteristic peaks.
Lead extraction in human sample by Zn2(BDC)2(DABCO) MOF Negar Motakef Kazemi et al
Fig. 3. FTIR spectra of MOF a) before and b) after lead adsorption.
10
3.3. FE-SEM images
The FE-SEM images were shown for MOF before
and after lead adsorption (Fig. 5). SEM results were
shown MOF nanoparticles with size of between
40-90 nm (before lead adsorption) and less than
100 nm (after lead adsorption). Lead absorption
was caused the increase of particle size due to
phenomenon of swelling. This result presented for
3.4. The Brunauer–Emmett–Teller (BET)
analysis
The Brunauer–Emmett–Teller (BET) analysis was
used for determination of surface area of MOF by
N
2
adsorption before and after lead adsorption (Fig.
6). The surface area of MOF was decreased with
lead adsorption from 762 m
2
g
-1
to 21 m
2
g
-1
. The
results indicate that there is almost no porosity after
lead.
Anal. Methods Environ. Chem. J. 4 (3) (2021) 5-20
Fig. 4. XRD Pattern of a) MOF, b) MOF after lead adsorption,
c) PCL polymer and d) MOF/PCL nanocomposite
11
Lead extraction in human sample by Zn2(BDC)2(DABCO) MOF Negar Motakef Kazemi et al
Fig. 5. FE-SEM images of a) MOF before lead adsorption before, b) MOF after lead adsorption,
and c) MOF/PCL nanocomposite in 200 nm scale bare.
12
3.5. Optimization study
The lead absorption was investigated by UV–Vis
spectroscopy. The calibration curve of lead was
max
= 208 nm with concentration of 0.1,
0.2, 0.4, 0.6, and 0.8 ppm (Fig. 7a). Lead adsorption
diagram was investigated by different MOF amount
including 0.1, 0.25, and 0.5 g for lead concentration at
0.6 ppm at various times (Fig. 7 b). Based on the result,
the increase of MOF amount was resulted to the increase
of lead adsorption due to increase of surface area.
The lead absorption was evaluated in different lead
concentrations by MOF and its nanocomposite at
different times (Fig. 8a). The lead concentrations were
included 0.4, 0.4, 0.8, and 1.0 ppm for absorption
investigation of 0.25 g MOF. The increase of lead
concentration was resulted to increase of adsorption
by MOF. The absorption of MOF/PCL nanocomposite
was examined at a constant concentration of 0.6 ppm
for lead solution (Fig. 8b). According to nanocomposite
result, the increase of MOF percentage was resulted
to increase of lead absorption. If fact, the increase of
MOF was created the higher lead absorption due to
increase of surface area.
Lead adsorption was studied in different pH of
solution including acidic (pH=2), neutral, and basic
(pH=10) for 0.25 g MOF with 0.6 ppm of lead
concentration and 10% nanocomposite with 0.6
ppm of lead concentration (Fig. 9). The higher pH
was caused more surface active sites, a competition
between positive charges(Pb), and increase lead
adsorption through the electrostatic force of
attraction. However, the optimum pH in ranging
from 7.5 to 8.5 for the divalent lead ions cased
improvement of chemical adsorption based on
nitrogen dative bond more than 95% and have less
than 32 % at pH 3-5 by physical adsorption.
Lead adsorption was evaluated in various
temperature including 25 (ambient), 40, 60, and
with 0.6 ppm of lead concentration (Fig. 10). The
increase of temperature was resulted to increase
of lead adsorption because of kinetic energy and
Brownian motion. Based on the previous report,
temperature is directly related to the potential for
adsorption by sorbent [19].
Anal. Methods Environ. Chem. J. 4 (3) (2021) 5-20
Fig. 6. The absorption/desorption N
2
curve related to MOF a) before and b) after lead adsorption.
13
Lead extraction in human sample by Zn2(BDC)2(DABCO) MOF Negar Motakef Kazemi et al
Fig. 7. a) The calibration curve of lead and b) the diagram of lead adsorption in
different MOF amount
14
Anal. Methods Environ. Chem. J. 4 (3) (2021) 5-20
Fig. 8. The diagram of lead adsorption by a) MOF and b) MOF/PCL
nanocomposite in different lead concentrations
15
Lead extraction in human sample by Zn2(BDC)2(DABCO) MOF Negar Motakef Kazemi et al
Fig. 9. The diagram of lead adsorption by a) MOF and b) MOF/PCL nanocomposite in different pH.
16
Anal. Methods Environ. Chem. J. 4 (3) (2021) 5-20
Fig. 10. The diagram of lead adsorption by a) MOF and b) MOF/PCL nanocomposite in different temperature.
17
Lead extraction in human sample by Zn2(BDC)2(DABCO) MOF Negar Motakef Kazemi et al
3.6. Validation of USA-S- µ-SPE / UV-Vis
By the USA-S- µ-SPE method, 50 mL of urine
and water samples were used for extraction and
determination lead ions by 0.25 g of MOF adsorbent
(0.05-1.0 mg L
-1
, 100-1000
-1
, pH=8). The
validated results were achieved for real samples by
spiking of the standard solution of lead (Pb) to 50
mL of samples. The recoveries of spiked samples
showed that the method was acceptable results for
lead extraction and determination in urine and water
samples. (Table 1) Also, the mean lead concentrations
were obtained (325.4± 13.8, n=5) by the ET-AAS
which was near to the USA-S- µ-SPE/UV-Vis
procedure (320.6± 15.2, n=5) as 98.4 % recovery.
methodologyfor lead adsorption by MOF.
4. Conclusions
In this research, the MOF and MOF/PCL
nanocomposite were used for lead adsorption.
The effect of different parameter including pH
and temperature of solution, Zn
2
(BDC)
2
(DABCO)
MOF and concentration of sorbent was shown
on lead adsorption by MOF and its PCL
nanocomposite. The results presented that MOF
and its PCL nanocomposite can represent an
economical source of lead sorbent from aqueous
solution to develop environmental applications.
The future prospects can be developed great
application of this nanocomposites.
The working range and the relative standard
deviation range (RSD%) for proposed procedure
were obtained 0.05-5 mg L
-1
and 2.13-5.24,
respectively (r = 0.9992). The absorption capacity
of Zn
2
(BDC)
2
(DABCO) MOF for standard lead
solution were ranged from 121.5 to 148.7 mg
g
-1
in optimized conditions. The method was
validated by the F-AAS.
Table 1. Validation of USA-S- µ-SPE/UV-Vis method for Pb(II) determination in urine and water samples based on
Zn
2
(BDC)
2
(DABCO) MOF adsorbent by spiking real samples
Sample* Added
(μg L
-1
)
*
Found (μg L
-1
) Recovery (%)
Well Water
--- 178.9 ± 7.2 ---
150 323.5 ± 15.6 96.4
Waste water
--- 397.8± 17.7 ---
500 903.6 ± 41.5 101.2
Waste water
--- 492.1 ± 22.3 ---
500 986.3± 44.6 98.8
Urine
--- 62.4 ± 2.8 ---
50 110.8± 4.7 96.8
Drinking water
--- ND ---
50 48.6 ± 2.1 97.2
--- 55.8 ± 2.4 ---
Urine 50 107.1 ± 3.3 102.6
ND: Not detected
18
5. Acknowledgements
The Authors gratefully acknowledge the research
council of Islamic Azad University and Department
of Medical Nanotechnology, Faculty of Advanced
Sciences and Technology, Tehran Medical Sciences,
Islamic Azad University, Tehran, Iran.
6. References
[1] P.B. Tchounwou, C.G. Yedjou, A.K. Patlolla,
D.J. Sutton, Heavy metals toxicity and the
environment, EXS J., 101 (2012) 133–164.
[2] A. Latif Wani, A. Ara, J. Ahmad Usmani,
Lead toxicity: a review, Interdiscip. Toxicol.,
8 (2015) 55–64.
[3] G. Flora, D. Gupta, A. Tiwari, Toxicity of
lead: a review with recent updates, Interdiscip.
Toxicol., 5 (2012) 47-58.
[4] M. Kosnett, Heavy metal intoxication and
chelators, Basic and clinical pharmacology,
10th ed, New York: McGraw-Hill, (2007) 945-
957.
[5] Agency for Toxic Substances and Disease
for Lead, Atlanta, GA: U.S. Department of
Health and Human Services, Public Health
Service, 2019.
[6] R. Arora, Adsorption of heavy metals–a
review, Mater. Today, 18 (2019) 4745-4750.
[7] J. Yang, B. Hou, J. Wang, B. Tian, J. Bi, N.
Wang, X. Li, X. Huang, Nanomaterials for the
removal of heavy metals from wastewater,
Nanomater., 9 (2019) 424. https://doi.
org/10.3390/nano9030424
S. Luque, J.R. Àlvarez, Recovery of heavy
metals from metal industry wastewaters by
chemical precipitation and
Desalination, 200 (2006) 742–744.
[9] MY. Vilensky, B. Berkowitz, A. Warshawsky,
In-situ remediation of groundwater
contaminated by heavy- and transition-metal
ions by selective ion-exchange methods,
Environ. Sci. Technol., 36 (2002) 1851–1855.
reverse osmosis for rejection of radioactive
isotopes and heavy metal cations from
drinking water sources, Desalination Water
Treat., 2 (2009) 342–350.
[11] S.B. Wang, H.W. Wu, Environmental-benign
J. Hazard. Mater., 136 (2006) 482–501.
[12] M. Odar, N. Motakef Kazemi,
Nanohydroxyapatite and its polycaprolactone
nanocomposite for lead sorbent from aqueous
solution, Nanomed. Res. J., (2020) Accepted.
[13] A. Alghamdi, AB. Al-Odayni, W. Sharaf
Saeed, A. Al-Kahtani, FA. Alharthi, T.
aqueous phase solutions using polypyrrole-
based activated carbon, Materials, 12 (2019)
2020.
[14] B. Feist, M. Pilch, J. Nycz, Graphene
10-phenanthroline as sorbent for separation
and preconcentration of trace amount of lead
(II), Microchim. Acta, 186 (2019) 91.
[15] M.R. Karim, M.O. Aijaz, N.H. Alharth, H.F.
Alharbi, F.S. Al-Mubaddel, M.R. Awual,
(vinyl alcohol)/chitosan for selective lead
(II) and cadmium (II) ions removal from
wastewater, Ecotoxicol. Environ. Safe., 169
(2019) 479-486.
[16] E. Kazemi, S. Dadfarnia, A.M. Haji
Shabani, P.S. Hashemi, Synthesis of
2-mercaptobenzothiazole/magnetic
nanotubes for simultaneous solid-phase
microextraction of cadmium and lead, Int. J.
Environ. Aanal. Chem., 97 (2017) 743-755.
[17] M. Mashkani, A. Mehdinia, A. Jabbari, Y. Bide,
M.R. Nabid, Preconcentration and extraction
of lead ions in vegetable and water samples by
N-doped carbon quantum dot conjugated with
Fe
3
O
4
as a green and facial adsorbent, Food
Chem., 239 (2018) 1019-1026.
[18] H. Shirkhanloo, S.D. Ahranjani, A lead
analysis based on amine functionalized
bimodal mesoporous silica nanoparticles
in human biological samples by ultrasound
Anal. Methods Environ. Chem. J. 4 (3) (2021) 5-20
19
assisted-ionic liquid trap-micro solid phase
extraction, J. pharm. Biomed. Anal., 157
(2018) 1-9.
[19] F. Ataei, D. Dorranian, N. Motakef-Kazemi,
Bismuth-based metal–organic framework
prepared by pulsed laser ablation method in
liquid, J. Theor. Appl. Phys., 14 (2020) 1–8.
[20] N. Motakef-Kazemi, M. Rashidian, S.
Taghizadeh Dabbagh, M. Yaqoubi, Synthesis
and characterization of bismuth oxide
nanoparticle by thermal decomposition of
bismuth-based MOF and evaluation of its
nanocomposite, Iran. J. Chem. Chem. Eng.,
40 (2021) 11-19.
[21] F. Ataei, D. Dorranian, N. Motakef-Kazemi,
Synthesis of MOF-5 nanostructures by laser
ablation method in liquid and evaluation of
its properties, J. Mater. Sci.: Mater. Electron.,
32 (2021) 3819–3833.
[22] B. Miri, N. Motakef-Kazemi, S.A.
Shojaosadati, A. Morsali, Application of a
nanoporous metal organic framework based
on iron carboxylate as drug delivery system,
Iran. J. Pharm. Res.,17 (2018) 1164–1171.
[23] H. Li, M. Eddaoudi, M. O’Keeffe, O. Yaghi,
Design and synthesis of an exceptionally
stable and highly porous metal-organic
framework, Nature, 402 (1999) 276–279.
Preparation and evaluation of ZnO
nanoparticles by thermal decomposition of
MOF-5, Heliyon, 5 (2019) e02152.
[25] N. Motakef-Kazemi, S.A. Shojaosadati, A.
Morsali, In situ synthesis of a drug-loaded
MOF at room temperature, Micropor.
Mesopor. Mater., 186 (2014) 73-79.
[26] N. Motakef-Kazemi, S.A. Shojaosadati,
A. Morsali, Evaluation of the effect of
nanoporous nanorods Zn
2
(bdc)
2
(dabco)
dimension on ibuprofen loading and release,
J. Iran. Chem. Soc., 13 (2016) 1205-1212.
[27] M.R. Mehmandoust, N. Motakef-Kazemi,
F. Ashouri, Nitrate adsorption from aqueous
solution by metal–organic framework MOF-
5, Iran. J. Sci. Technol. A, 43 (2019) 443–449.
[28] N. Motakef-Kazemi, A novel sorbent based
on metal–organic framework for mercury
separation from human serum samples by
ultrasound assisted-ionic liquid-solid phase
microextraction, Anal. Methods Environ.
Chem. J., 2 (2019) 67-78.
[29] H. Nabipour, B. Soltani, N. Ahmadi Nasab,
Gentamicin loaded Zn
2
(bdc)
2
(dabco)
delivery and antibacterial activity, J. Inorg.
Organomet. Polymer Mater., 28 (2018)
1206–1213.
[30] K. Xie, Y. He, Q. Zhao, J. Shang, Q. Gu,
GG. Qiao, PA. Webley, Pd(0) loaded
Zn
2
(azoBDC)
2
(dabco) as a heterogeneous
catalyst, Cryst. Eng. Comm., 19 (2017) 4182-
4186.
[31] I. Senkovska, S. Kaskel, High pressure
methane adsorption in the metal-organic
frameworks Cu
3
(btc)
2
, Zn
2
(bdc)
2
dabco, and
Cr
3
F(H2O)
2
O(bdc)
3
, Micropor. Mesopor.
Mat., 112 (2008) 108–115.
[32] A. Schneemann, V. Bon, I. Schwedler, I.
Senkovska, S. Kaskel, R.A. Fischer, Flexible
metal–organic frameworks, Chem. Soc. Rev.,
43 (2014) 6062-6096.
[33] N.S. Behbahani, K. Rostamizadeh, M.R.
Yaftian, A. Zamani, H. Ahmadi, Covalently
PEG: Preparation and characterization as
nano-adsorbent for removal of lead from
wastewater, J. Environ. Health Sci., 12 (2014)
103.
[34] R. Ricco, K. Konstas, MJ. Styles, J.J.
Richardson, R. Babarao, K. Suzuki, P.
Scopece, P. Falcaro, Lead(II) uptake by
aluminium based magnetic framework
composites (MFCs) in water, J. Mater. Chem.
A, 3 (2015) 19822–19831.
[35] Y. Wang, J. Xie, Y. Wu, H. Gea, Z. Hu,
Preparation of a functionalized magnetic
metal–organic framework sorbent for the
extraction of lead prior to electrothermal
atomic absorption spectrometer analysis, J.
Mater. Chem. A, 1 (2013) 8782-8789.
Lead extraction in human sample by Zn2(BDC)2(DABCO) MOF Negar Motakef Kazemi et al
20
[36] J. Shen, N. Wang, Y. Guang Wang, D. Yu,
from aqueous solutions by metal organic
framework (Zn-BDC) coated magnetic
montmorillonite, Polymers, 10 (2018) 1383.
[37] Y.L.F. Musico, C.M. Santos, M.L.P. Dalida,
D.F. Rodrigues, Improved removal of lead(II)
from water using a polymer-based graphene
oxide nanocomposite, J. Mater. Chem. A, 1
(2013) 3789–3796.
[38] M. Irandoost, M. Pezeshki-Modaress, V.
Javanbakht, Removal of lead from aqueous
nanoclay and nanozeolite, J. Water Process
Eng., 32 (2019) 100981.
[39] KM. Seema, BB. Mamba, J. Njuguna, RZ.
Bakhtizin, AK. Mishra, Removal of lead (II)
from aqueous waste using (CD-PCL-TiO
2
)
bio-nanocomposites, Int. J. Biol. Macromol.,
109 (2018) 136-142.
[40] H.R. Cadorim, M. Schneider, J. Hinz, F.
Luvizon, A.N. Dias, E. Carasek, B. Welz,
Effective and high-throughput analytical
methodology for the determination of lead
and cadmium in water samples by disposable
pipette extraction coupled with high-
resolution continuum source graphite furnace
atomic absorption spectrometry (HR-CS GF
AAS), Anal. Lett., 52 (2019) 2133-2149.
[41] N. Mouhamed, K. Cheikhou, G.E.M. Rokhy,
D.M. Bagha, M.-D.C. Guèye, T. Tzedakis,
Determination of lead in water by linear sweep
anodic stripping voltammetry (LSASV)
optimization of operating parameters, Am. J.
Anal. Chem., 9 (2018) 171.
[42] H. Shirkhanloo, A. Khaligh, H.Z. Mousavi,
A. Rashidi, Graphene oxide-packed micro-
column solid-phase extraction combined with
determination of lead (II) and nickel (II) in
water samples, Int. J. Environ. Anal.Chem.,
95 (2015) 16-32.
[43] S. Azimi, Z. Eshaghi, A magnetized
nanoparticle based solid-phase extraction
procedure followed by inductively coupled
plasma atomic emission spectrometry to
determine arsenic, lead and cadmium in
water, milk, Indian rice and red tea, Bull.
Environ. Contam. Toxicol., 98 (2017) 830-
836.
[44] Y. Huang, S. Lia, J. Chen, X. Zhang, Y.
Chen, Adsorption of Pb(II) on mesoporous
activated carbons fabricated fromwater
hyacinth using H
3
PO
4
activation: Adsorption
capacity kinetic and isotherm studies, Appl.
Surf. Sci., 293 (2014) 160– 168.
[45] M. Borjigin, C. Eskridge, R. Niamat, B.
Strouse, P. Bialk, E.B. Kmiec, Electrospun
8 (2013) 855–864.
Anal. Methods Environ. Chem. J. 4 (3) (2021) 5-20
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Cobalt separation from water and food samples based
on penicillamine ionic liquid and dispersive liquid-
liquid microextraction before determination by AT-FAAS
Yaghoub Pourshojaei
a,*
and Alireza Nasiri
b
a
Department of Medicinal Chemistry, Faculty of Pharmacy, Kerman University of Medical Sciences, Kerman, Iran.
b
Environmental Health Engineering Research Center, Kerman University of Medical Sciences, Postal code:7619813159, Kerman, Iran
ABSTRACT
The cobalt compounds have adverse health effect on human and
caused to damage of the DNA cells, neurological and endocrine
systems. Therefore, the separation and determination of cobalt in
water and food samples must be considered. In this research, the
(2S)-2-amino-3-methyl-3-sulfanylbutanoic acid (penicillamine) as a
chelating agent mixed with ionic liquid (OMIM PF
6
) /acetone and
used for extraction of cobalt from 50 mL of water samples by ultra-
assisted dispersive liquid-liquid microextraction (USA-DLLME) at
pH=6. Based on procedure, the samples were shaked for 5 min (25
o
C)
and after complexation of cobalt ions by thiol and amine group of
penicillamine, the ionic liquid phase separated in the bottom of the
conical tube by centrifuging for 3.0 min. The upper liquid phase
was vacuumed by the auto-sampler and the Co
2+
ions back extracted
from the ionic liquid/ penicillamine in acidic pH. Finally, the cobalt
atomic absorption spectrometry (AT-FAAS). The main parameters
such as the sample volume, the penicillamine amount, the ionic liquid
amount and the shaking time were optimized. The linear range, the
detection limit (LOD) and enrichment factor were obtained 1.5-62
L
-1
, 0.38 L
-1
and 98.5, respectively (r = 0.9995, RSD%=2.2). The
procedure was validated by ET-AAS analysis.
Keywords:
Cobalt,
Water and food,
Penicillamine,
Ionic liquid,
Ultra-assisted dispersive liquid-
liquid microextraction,
spectrometry
ARTICLE INFO:
Received 11 Jun 2021
Revised form 8 Aug 2021
Accepted 30 Aug 2021
Available online 28 Sep 2021
*Corresponding Author: Yaghoub Pourshojaei
Email: pourshojaei@yahoo.com
https://doi.org/10.24200/amecj.v4.i03.148
------------------------
1. Introduction
Cobalt compounds exist in two valence forms include
cobalt (Co II, cobaltous, Co
2+
and Co III, cobaltic,
Co
3+
), the other forms have not environmentally
available. Also, the other cobalt compounds have
toxic effect in the environment and the human body
by extra exposure [1]. The people is exposed to cobalt
through inhalation of air and food and drinking water.
Cobalt ions enter to environment from numerous
industrial factories such as heavy metals activity
process, the grinding, the mining and paint [2].
Furthermore, it can be used for a medical process for
the medicine Company. The cobalt compounds are
widely dispersed in air with a low concentration less
than 2.0 ng m
-3
[3, 4]. Cobalt has a low concentration
range between 0.1-5 L
-1
in drinking water. The
cobalt concentration in river, the groundwater, the
-1
[5].
Feng et al reported the concentrations of cobalt in
the groundwater had lower than 0.01 mg L
-1
which is
lower than other heavy metals [6]. Lim et al showed
an applied model for the heavy metals such cobalt in
22
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
[7]. United
States Environmental Protection Agency (EPA)
reported that the cobalt levels in sediment and surface
-1
-1
, , respectively
[2]. Food analysis in dietary cobalt intake such as
to control cobalt toxicity in human body which is
[8]. Besides, the
skin contact is a main way that cobalt was entered to
human body. Cobalt as an essential metal exists in the
human body and the maximum amount of it generally
concentrated in the liver. Cobalt in eggs has biological
role in vitamin B12 and named cyanocobalamin [9].
It uses in structure of vitamin B
12
and produce the red
[9]. Cobalt toxicity cause several health problems
such as cardiomyopathy, nerve/thyroid problems,
hearing and visual impairment, neuropathy,
tinnitus
and glomerulonephritis [10, 11]. Therefore, the
accurate results for determination of cobalt must
be considered by a new technology. The normal
concentration of cobalt is equal to 1.0 ng mL
-1
for
environmental or occupational exposure and more
than this value cause to toxicity. The sources
of cobalt can be entering to human body from
occupational/environmental/food exposures. The
blood Co concentration is 100 µgL
-1
and more than
300 µgL
-1
cause toxicity in human [12, 13]. The
penicillamine a chelating agent, is a trifunctional
compound, containing of a thioalcohol, a carboxylic
acid, and an amine that was used for the treatment
of Wilson’s disease, kidney stones , rheumatoid
arthritis, and removal of heavy metal. Based on
disorder of copper metabolism, copper accumulated
in human body and the penicillamine extracted
extra copper from body but, it can be removed the
other essential metals from body [14, 15]. Many
analytical methods such as electrothermal atomic
absorption spectrometry (ET-AAS) [16],
atomic absorption spectrometry (F-AAS) [17] and
the inductively coupled plasma optical emission/
mass spectrometry (ICP-OES, ICP-MS) [18] have
previously used for the determination of cobalt in
various water and food samples. Moreover, analytical
techniques based on the above instruments cannot
For this purpose, the procedures must be developed
for the separation and preconcentration of cobalt
from samples. There are many methodologies for
matrixes including,
the magnetic solid phase extraction (MSPE) [19],
dispersive micro-solid phase extraction (D-
[20], the liquid-liquid extraction (LLE), the dispersive
liquid-liquid microextraction (DLLME) [21], the
electrochemistry methods (ECM) [22], the cloud
point extraction (CPE) [23] and the precipitation
[24]. Recently, the ultra-assisted dispersive liquid-
liquid microextraction (USA-DLLME) [25] has
been used as one of the most practical methods for
the separation of metal ions. The main advantages
of USA-DLLME to other techniques are simple
separation, high preconcentration, fast analysis, low
time, high recovery and good enrichment factor (EF).
The ionic liquid as green solvent plays critical role for
collection of ligand and metals from samples into two
phases; a IL/ligand phase and liquid phase of water
samples. Metal ions can be extracted from aqueous
solution into the small-volume IL/ligand phase with
hydrophobicity, the more density than water samples
and low solubility in water. In this study, the mixture
of (2S)-2-amino-3-methyl-3-sulfanylbutanoic acid
(penicillamine)/ (OMIM PF
6
) /acetone have been
used for extraction of cobalt from water samples
by USA-DLLME at pH=6. The thiol and amine
groups of penicillamine play an important role in the
coordination of metals and have a strong complex
with the cobalt ions [26]. In this study, this ligand
was used as an ion carrier and as a chelating agent to
cobalt ions accompanied with ionic liquid
2. Experimental
2.1. Instrumental Analysis
The cobalt (Co) value in water and digested food
samples was determined by AT-FAAS (GBC, Aus).
The air-acetylene was used for cobalt measurement by
AT-FAAS. The atom trap accessory as SQT-AT devices
is placed on the burner. In order to improve sensitivity,
SQT which the source beam was passed. SQT-AT
devices cause to increase the sensitivity of absorption
23
Cobalt extraction by penicillamine and ionic liquid Yaghoub Pourshojaei et al
(ABS) per concentration before analysis. The limits
of detection (LOD) were obtained at 0.05 and 0.13
mg L
-1
for the AT-FAAS and FAAS, respectively. The
HCL was adjusted by screws up to maximum energy.
The AT-FAAS for cobalt determination was tuned by
wavelength of 240.7 nm (7 mA). The aspiration of
samples into FAAS was done by the auto-sampler
(0.5-1 mL). The linear range for AT-FAAS was 0.15-
6.0 mg L
for cobalt analysis. The working range for
the AT-FAAS and F-AAS was obtained at 0.15-15
and 0.4-15 mg L
for cobalt, respectively. Graphite
furnace accessory coupled to an atomic absorption
spectrophotometer (GBC) was used for validation of
cobalt in digested food and water samples. The pH of
the samples was adjusted by favorite buffer solutions
(Sigma, Germany) and determined by the Metrohm
pH meter (Swiss). The phosphate buffers (Na
2
HPO
4
and NaH
2
PO
4
) were used to adjust the pH from 6.0
to 8.0.
2.2. Reagents and Materials
The ultra-pure H
2
SO
4
, HCl, NaOH and HNO
3
solutions for cobalt analysis in food and water
samples were prepared from Sigma Aldrich
(Germany). The calibration solutions of Co(II) were
made by dissolving 1.0 g of cobalt nitrate (Co(NO
3
)
2
)
in 1 L of deionized water (DW) solution (2% HNO
3
).
The linear ranges of cobalt were daily prepared by
standard solutions (1g L
-1
, 1000 mg L
-1
) and diluted
by DW (Millipore, USA). All of the laboratory
glassware was cleaned with nitric acid (5% v/v)
and washed with DW for 10 times. ionic liquid of
(HMIM PF
6
, CAS N: 304680-35-1), 1-Methyl-3-
[PF
6
], CAS N: 304680-36-2), 1-methyl-3-
[PF
6
], [BMIM][PF6], CAS N: 304680-36-2), and
( [EMIM][PF
6
], CAS N: 155371-19-0), acetone
(CAS N: 67-64-1) and the penicillamine (CAS N:
52-66-4) were purchased from Sigma, Germany.
The reagents of Na
2
HPO
4
and NaH
2
PO
4
(CAS N:
7558-79-4, 99.95%; CAS N: 7558-80-7, 99%) were
prepared from the Sigma Aldrich, Germany.
2.3. Preparation of water and food samples
All food samples (Rice, Spinach, Broccoli, and
Onion) were pulverized and then ground/ dried/
homogenized before analysis. Finally, the powder
samples are converted to a uniform size and then
place in the oven at 90
C for 3 h. After adding DW
to food samples, the homogenization of sample
was digested with microwave (Antom Paar, multi-
wave) based on book catalog procedure. The food
samples were digested at optimum conditions
(200
C, 500 ps UV radiation). First, 1.0 g of food
powder samples were placed in PTFE tube with
surrounding ceramic tube of microwave and then, 5
mL of HNO
3
with 1 mL of H
2
O
2
solution were added
to samples. The powder samples were digested for
58 min and diluted with DW up to 50 mL before
determination of cobalt by the USA-DLLME at
pH=6. By microwave, the all cobalt forms in foods
(organic foods) convert to Co(II) by induced oxygen
combustion and total cobalt can be determined in
food samples. All water samples prepared based on
3
(2%) by
the ASTM sampling method for water and storage in
PE tube at -4
0
C.
2.4. Procedure of cobalt extraction
The Co (II) ions were separated and preconcentrated
based on the complexation of cobalt-penicillamine
in water and food samples by the USA-DLLME
procedure (Fig.1). Also, the total cobalt in food
samples was determined based on penicillamine
ligand by the AT-AAS. The penicillamine (0.12 g)
dispersed into 180 mg of hydrophobic ionic liquid
([HMIM][PF
6
] and 0.5 mL acetone and then, the
mixture of ligand/([HMIM][PF
6
] /acetone was
injected into 50 mL of water or standard solution
of cobalt (1.5-62 L
-1
) by a syringe at pH=6.
After sonication of samples for 5.0 min, the
Co(II) ions were complexed by the thiol group of
(2S)-2-amino-3-methyl-3-sulfanylbutanoic acid].
After the extraction process, the Co-ligand was
trapped in the hydrophobic [HMIM][PF
6
] at the
bottom of a conical PE tube by centrifuging for
5 min (3500 rpm). The upper liquid phase was
24
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
evacuated and the Co ions were back-extracted
from ligand/([HMIM][PF
6
] into an aqueous phase
by 0.25 mL of HNO
3
(0.5M) and diluted with
DW up to 0.5 mL. Finally, the Co concentration
in the remaining solution was determined by the
AT-FAAS. In addition, 1.0 g of food powder was
added to HNO
3
/H
2
O
2
solution (5:1) in the PTFE
vials and samples were digested at 58 min based
on the induced oxygen combustion/UV radiation.
The digested food samples are diluted with DW up
to 50 mL before cobalt analysis by the AT-F-AAS
based on same procedure by ligand/([HMIM]
[PF
6
] /acetone at pH=6.
3. Results and Discussion
By the USA-DLLME procedure, the preconcentration/
separation of Co (II) ions in water samples was
occurred for different cobalt concentrations as a
lower range (1.5 L
) and upper range (62
L
) by the penicillamine ligand. Moreover, the total
cobalt extracted from digested food samples such
rice, spinach, broccoli and onion before determined
by the AT-FAAS. The mechanism of extraction is
based on the interaction of nitrogen(--NH) and thiol
(--SH) groups of the penicillamine with cobalt ions
using dative/covalent bonding (Schema 1). The
ion in water/food samples was performed by the
Fig.1. Cobalt extraction based on the complexation of penicillamine in water and food samples
by the USA-DLLME procedure
Schema 1. The mechanism of extraction between nitrogen and thiol of the penicillamine with cobalt ions
25
Cobalt extraction by penicillamine and ionic liquid Yaghoub Pourshojaei et al
penicillamine ligand under optimized conditions
such as the amount of the penicillamine ligand,
pH, ionic liquids content, sample volume, and
interfering ions
3.1. Amount of ligand
In the presented procedure, the amount of
penicillamine as a ligand was optimized for
separation/extraction of cobalt from the water
and digested food samples. Thus, the amounts of
penicillamine on cobalt extraction were studied in
the range of 0.02-0.3 g in the presence of cobalt
concentration (1.5-62 L
-1
) for 50 mL of liquid
samples. The results showed that the quantitative
extraction was obtained at 0.10 g of penicillamine.
amount of ligand which was added to IL /acetone
as an extraction phase for water and food samples.
Also, the effects of ILs on the extraction of cobalt
were examined without any ligand and the recovery
of ILs for cobalt was achieved less than 5%. Due
to Figure 2,
complexation of penicillamine more than 95%.
3.2. Amount of ionic liquids/acetone
By the USA-DLLME procedure, the effects of
different ionic liquids, [OMIM][PF
6
], [BMIM][PF6]
[HMIM][PF
6
] and [EMIM][PF
6
] were studied as
trapping agents for cobalt extraction. So, the amounts
of the hydrophobic ILs on the cobalt extraction were
evaluated in the range of 20-250 mg of ILs containing
1.5-62 L
-1
of cobalt for 50 mL of water and digested
food samples at pH=6. The quantitative recovery was
achieved for cobalt with 160 mg [OMIM][PF
6
]. So,
180 mg of [OMIM][PF
6
] was used as an optimal IL
for water and food samples. In addition, the effects
of [OMIM][PF
6
] for cobalt extraction were evaluated
without any ligand and the maximum recovery
was obtained less than 5%. Therefore, the [OMIM]
[PF
6
recovery can be collecting cobalt –ligand from the
liquid phase (Fig. 3).
Fig.2. The effect of amount of penicillamine ligand on cobalt extraction
0.05 0.1 0.15 0.2 0.25 0.3 0.35
26
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
3.3. Sample volume
Sample volume is the main parameters for cobalt
extraction in water and foods samples which must be
optimized. Therefore, the different sample volumes
for cobalt extraction/separation/preconcentration in
water and foods samples between 5-100 mL based
on penicillamine ligand were studied containing
1.5-62 L
-1
of cobalt. According to Figure 4, the
water and food samples at pH=6. So, 50 mL of water
or digested food samples were selected as an optimal
volume by the USA-DLLME procedure (Fig. 4).
Fig.3. The effect of amount of IL on cobalt extraction by the USA-DLLME procedure
Fig.4. The effect of sample volume on cobalt extraction by the USA-DLLME procedure
20 50 100 120 160 180 200 250
27
Cobalt extraction by penicillamine and ionic liquid Yaghoub Pourshojaei et al
3.4. pH Effect
pH is one of the most important parameters for
cobalt extraction in water and digested food
samples Therefore, the pH ranges from 2 to 10
was prepared and adjusted by buffer solution for
recovery based on penicillamine ligand /IL was
observed for cobalt concentrations (1.5-62 L
-1
)
at pH of 5.5-6.5 in water samples. So, pH 6.0 was
used for extraction of cobalt in water and digested
food samples by the USA-DLLME procedure
(Fig. 5). The proposed mechanism of cobalt
extraction has been shown in the Schema 1 based
on dative/covalent bond of thiol (HS) and amine
(NH
2
) functional groups of penicillamine with the
positive charge of cobalt (Co
2+
) at pH 6.0. Due
to results, the isoelectric pH of penicillamine is
4.85, it can be concluded that above this pH, the
amine and thiol groups of peniclamine are free
and they have nucleophilic ability to attack to
orbitals of cobalt ion, and they easily participate
in the complex formation process to extract
cobalt ion. So in acidic pH, the (NH
2
) group of
penicillamine ligand has positive charged (NH
3
+
)
and the complexation wasn’t occurred due to
electrostatic repulsion between Co
2+
and NH
3
+
,
if some complexation is formed, it is due to the
participation of the thiol group in this process.
Also, the observed decline in the Figure 5 at pH
above of 6.5 may be due to the competition of
hydroxyl ions with the penicillamine ligand for
complex formation resulting in the formation of
stable cobalt hydroxide. So, the complexation of
penicillamine ligand with Co
2+
ions
decreased at
more than pH=6.5 as participated cobalt ions by
hydroxide form (Co(OH)
2
).
Fig.5. The effect of pH on cobalt extraction at LLOQ (Blue) and ULOQ (green)
by the USA-DLLME procedure
2 3 4 5 5.5 6 6.5 7 8 9 10
28
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
3.5. Effect of interference of ions
The effect of interference ions on cobalt
extraction based on penicillamine ligand in
water/food samples was evaluated by the USA-
DLLME procedure. So, the main concomitant
ions were studied in water and food samples
with different concentrations between 0.5-
3 mgL
-1
for 50 mL of samples at pH=6. The
results showed that the interfering ions had not
affected for the cobalt extraction in water/food
samples by the proposed procedure (Table 1).
Also, the concentration ratio of interfering ions/
cobalt ions (C
M
/C
Co
) for water ranged between
100-1800. The mean ratios for mercury, nickel
and lead were seen at about 100-200, 700-850,
600-800 in water and digested food samples,
respectively. So, the penicillamine ligand/ionic
liquid phase can be extracted cobalt ions in the
presence of the main interfering ions.
3.6. Eluent concentration and volume
The various eluents such as HNO
3
, HCl and H
2
SO
4
were used for back extraction of cobalt ions from the
penicillamine ligand/IL/acetone. At acidic pH, the
complexation of Co…SH-P was broken down and
cobalt ions released into acid solution. Therefore, the
various acid solutions based on different volumes and
concentrations (0.2-1 mol L
-1
, 0.1-1 mL were used
for cobalt back extraction from IL phase. The Co(II)
ions were quantitatively back-extracted from the
penicillamine ligand/IL by HNO
3
with concentration
more than 0.4 M. So, the 0.5 mol L
-1
of HNO
3
solution
was selected as an eluent. Moreover, the various
volumes of eluents between 0.1-1 mL were used for
back-extraction of cobalt ions in water/food samples.
Due to Figure 6, the 0.25 mL of HNO
3
(0.5 M) had the
Finally, the remained solution was diluted with DW
up to 0.5 mL before determining by AT-FAAS.
Table 1. The effect of interfering ions on extraction of Co(II) in water and digested food samples
by the USA-DLLME procedure
Interfering Ions in blood (M)
Mean ratio
(C
M
/C
Co(II)
)
Recovery (%)
Co(II) Co(II)
Cr
3+
, Al
3+
, Fe
3+
750 97.0
Mn
2+
, Cd
2+
, Mo
2+
800 96.6
Pb
2+
700 99.4
Zn
2+
, Cu
2+
600 97.8
I
-
, Br
-
, F
-
, Cl
-
1200 97.4
Na
+
, K
+
, Ca
2+
, Mg
2+
1400 98.1
CO
3
2-
, PO
4
3-
, HCO3
-
, SO
4
2-
1000 99.2
Ni
2+
800 97.9
NH
4
+
, SCN
-
, NO
3
-
900 98.3
Hg
2+
150 97.2
29
Cobalt extraction by penicillamine and ionic liquid Yaghoub Pourshojaei et al
3.7. Real sample analysis
The extraction of cobalt (II) ions with the
penicillamine ligand in water/food samples were
developed by the USA-DLLME procedure at pH 6.
Also, the total Co(II) in rice, spinach, broccoli and
onion was determined after the digestion process by
proposed procedure. The total Co(II) determined
in digested foods samples after extraction by the
penicillamine ligand/[OMIM][PF
6
] at pH 6.0.
Moreover, the real water and food samples were
validated by spiking of standard solutions of cobalt
in optimized conditions (Table 2). Therefore, the
various concentrations of Co(II) were spiked to
real samples. The results showed us that the high
recovery for Co(II) ions in water/food samples was
created by 1.2 g of the penicillamine ligand and
150 mg of [OMIM][PF
6
].
Based on Table 2
and the satisfactory results was demonstrated
the penicillamine ligand/[OMIM][PF
6
] can
be obtained the accurate and precision results
for cobalt in liquid samples. Also, the method
validation was achieved based on the ET-AAS and
the ICP –MS analyzer by microwave digestion
process (Table 3).
4. Conclusions
A simple and sensitive method based on
the penicillamine ligand/[OMIM][PF
6
] was
obtained for the Co (II) ions determination in
water and digested food samples at pH=6. The
concentrations of cobalt ions were determined
by the AT-FAAS detection method after sample
preparation by the USA-DLLME procedure.
Recovery was achieved between 95.2–103.6 and
relative standard deviation (RSD%) between 1.9-
4.5 under optimized conditions. In this procedure,
the shaking and centrifuging time were 4.5 and
3.0 minutes, respectively. The working range of
1.5-153 L
were achieved by the presented
method. Therefore, cobalt ions were extracted
and determined effectively using penicillamine
ligand/[OMIM][PF
6
] in water/food samples with
the USA-DLLME coupled to AT-FAAS.
Fig.6. The effect of eluents on cobalt extraction by the USA-DLLME procedure
0/2 0/3 0/5 0/6 0/8 1
0.2 0.3 0.5 0.6 0.8 1
30
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
Table 2. Validation of methodology for Co(II) determination with penicillamine ligand/[OMIM][PF
6
]
based on spiking standard samples by the USA-DLLME procedure coupled to AT-FAAS
Sample* Added
(μg L
-1
)
*
Found W (μg L
-1
)/F(μg g
-1
) Recovery (%)
Well water A
--- 12.1 ± 0.4 ---
10 21.9 ± 0.9 98.0
Wastewater B
--- 45.6 ± 2.3 ---
50 95.2 ± 4.5 99.2
Wastewater C
--- 34.5 ± 1.7 ---
50 85.2 ± 3.9 101.4
Rice
--- 21.2 ± 0.8 ---
20 40.9 ± 1.6 98.5
Spinach
--- 24.6 ± 1.1 ---
25 49.2 ± 2.3 98.4
--- 30.2 ± 1.2 ---
Broccoli 30 60.8 ± 2.4 102
--- 27.8 ± 1.3 ---
Onion 30 57.3 ± 2.7 98.3
Food samples digested by Microwave and determined by proposed procedure
All food samples prepared from supermarket Tehran
Well water A: 25 mL of water prepared from Shahre Ray, Tehran
Wastewater B: 25 mL of water prepared from petrochemical industry, Tehran, Iran
Wastewater C: 25 mL of water prepared from paint factory, Arak, Iran
-1
-1
-1
)
Table 3. The comparing of USA-DLLME /AT-FAAS method with ET-AAS and ICP –MS
for cobalt determination in water and digested food samples (Mean, water ( L
-1
)/ Food ( g
-1
), n=20)
Sample
ψ
ICP-MS ET-AAS
ψ ψ
USA-DLLME r* r֎
Wastewater A 11.9 ± 0.1 12.6 ± 0.3 12.3 ± 0.4 0.77 0.70
Wastewater B 46.1 ± 0.9 44.9 ± 2.3 45.5 ± 2.4 0.81 0.73
Rice 21.6 ± 0.5 20.6 ± 1.0 21.3 ± 0.8 0.65 0.78
Spinach 24.1 ± 0.8 25.3 ± 1.3 24.6 ± 1.1 0.62 0.81
Onion 26.9 ± 0.7 29.1 ± 1.5 27.6 ± 1.3 0.59 0.74
*r: Correlation of ET-AAS with USA-DLLME /AT-FAAS method for cobalt determination (n=20)
֎
r: Correlation of ICP-MS with USA-DLLME /AT-FAAS method for cobalt determination (n=20)
*Mean of three determinations of samples , n=20)
31
Cobalt extraction by penicillamine and ionic liquid Yaghoub Pourshojaei et al
5. Acknowledgments
The authors wish to thank from Department
of Medicinal Chemistry, Faculty of Pharmacy,
Kerman University of Medical Sciences, Kerman,
Iran and Environmental Health Engineering
Research Center, Kerman University of Medical
Sciences, Kerman, Iran.
6. References
[1] D. J. Paustenbach, B. E. Tvermoes, K. M.
Unice, B. L. Finley, B. D. Kerger, A review of
the health hazards posed by cobalt, Crit. Rev.
Toxicol., 43 (2013) 316–362.
[2] J. E. Gray, R. G. Eppinger, Distribution of Cu,
Co, As, and Fe in mine waste, sediment, soil,
and water in and around mineral deposits and
mines of the Idaho Cobalt Belt, USA, Appl.
Geochemistry, 27 (2012) 1053–1062.
[3] H. P. Hutter, P. Wallner, H. Moshammer, G.
Marsh, Dust and cobalt levels in the austrian
tungsten industry: workplace and human
biomonitoring data, Int. J. Environ. Res. Public
Health, 13 (2016) 931-938.
[4] M. Klasson, I. Bryngelsson, C. Pettersson,
B. Husby, H. Arvidsson, H. Westberg,
Occupational exposure to cobalt and tungsten
in the swedish hard metal industry: air
concentrations of particle mass, number, and
surface area, Ann. Occup. Hyg., 60 (2016)
684–699.
[5] World Health Organization (WHO),
Guidelines for drinking water quality, 3
rd
edn.
World Health Organization, Geneva, 2011.
https://www.who.int/publications-detail-
redirect/9789241549950.
[6] S. Feng, X. Wang, G. Wei, P. Peng, Y. Yang,
Z. Cao, Leachates of municipal solid waste
incineration bottom ash from Macao: Heavy
metal concentrations and genotoxicity,
Chemosphere, 67 (2007) 1133–1137.
[7] S. R. Lim, J. Schoenung, Human health and
ecological toxicity potentials due to heavy
metal content in waste electronic devices with
(2010) 251–259.
[8] M. Moghadam, S. Jahromi, A. Darehkordi,
Simultaneous spectrophotometric
determination of copper, cobalt, nickel and
iron in foodstuffs and vegetables with a
new bis thiosemicarbazone ligand using
chemometric approaches, Food Chem., 192
(2016) 424–431.
vitamin B12 and cobalt in egg yolk using
vortex assisted switchable solvent based liquid
phase microextraction prior to slotted quartz
Food Chem., 286 (2019) 500–505.
[10] K. A. Fox, T. M. Phillips, J. H. Yanta, M. G.
Abesamis, Fatal cobalt toxicity after total hip
arthroplasty revision for fractured ceramic
components, Clin. Toxicol., 54 (2016) 874–
877.
[11] A. Cheung, Systemic cobalt toxicity from total
hip arthroplasties: review of a rare condition
Part 1 - history, mechanism, measurements,
and pathophysiology, Bone Joint J., 98 (2016)
6–13.
[12] B. Tvermoes, B. Finley, K. Unice, J. Otani,
D. Paustenbach, D. Galbraith, Cobalt whole
blood concentrations in healthy adult male
volunteers following two-weeks of ingesting
a cobalt supplement., Food Chem. Toxicol.,
53 (2012) 432-439.
[13] A. Hart, P. Buddhdev, P. Winship, N. Faria, J.
J. Powell, J. Skinner, Cup inclination angle of
greater than 50 degrees increases whole blood
concentrations of cobalt and chromium ions
after metal-on-metal hip resurfacing, HIP Int.,
18 (2008) 212–219.
of histamine based on aggregation-induced
emission, Microchim. Acta, 18 (2020) 7329.
[15] Y. Hong, S. Jo, J. Park, J. Park, J. Yang, High
sensitive detection of copper II ions using
D-penicillamine coated gold nanorods based
on localized surface plasmon resonance,
Nanotechnol., 29 (2018) 215501.
32
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-32
and sensitive analytical method based on
vortex assisted deep eutectic solvent-liquid
phase microextraction for the determination
absorption spectrometry, Food Chem., 310
(2020) 125825.
[17] M. Shirani, F. Salari, S. Habibollahi, A. Akbari,
Needle hub in-syringe solid phase extraction
based a novel functionalized biopolyamide
for simultaneous green separation/
preconcentration and determination of cobalt,
nickel, and chromium (III) in food and
environmental samples with micro sampling
Microchem. J., 152 (2019) 104340.
[18] M. Asli, M. Azizzadeh, A. Moghaddamjafari,
M. Mohsenzadeh, Copper, iron, manganese,
zinc, cobalt, arsenic, cadmium, chrome, and
lead concentrations in liver and muscle in
Iranian Camel (Camelus dromedarius), Biol.
Trace Elem. Res., 194 (2020) 390–400.
[19] S. G. Elci, Determination of cobalt in food
by magnetic solid-phase extraction (MSPE)
preconcentration by polyaniline (PANI)
and polythiophene (PTH) coated magnetic
nanoparticles (MNPs) and microsample
spectrometry (MIS-FAAS), Instrum. Sci.
Technol., 49 (2021) 258–275.
[20] F. Salimi, M. Shamsipur, E. Koosha, M.
Ramezani, A new dispersive micro-solid
phase extraction based on rejection property
method combined with FAAS for the
simultaneous determination of cobalt and
copper after optimisation by Box-Behnken
design, Int. J. Environ. Anal. Chem., (2020)
1–13.
[21] Q. Han, Y. Huo, X. Yang, Y. He, J. Wu,
Dispersive liquid–liquid microextraction
coupled with graphite furnace atomic absorption
spectrometry for determination of trace cobalt
in environmental water samples, Int. J. Environ.
Anal. Chem., 100 (2020) 945–956.
[22] H. Kang, J. Li, C. Zhang, J. Lu, Q. Wang, Y.
Wang, Study of the electrochemical recovery
of cobalt from spent cemented carbide, RSC
Adv., 10 (2020) 22036–22042.
[23] R. Kakitha, S. Pulipaka, D. Puranam,
Simultaneous determination of iron and cobalt
using spectrophotometry after catanionic mixed
micellar cloud point extraction procedure,
Orient. J. Chem., 36 (2020) 1168–1172.
[24] K. Kafumbila, Cobalt precipitation with MgO:
material balance from kinetic samples cobalt
precipitation with MgO: Material balance from
kinetic samples. Independent Metallurgical
Operations Pty Ltd (IMO), 2020.
[25] A. Ghasemi, M. R. Jamali, Z. Es’haghi,
liquid phase microextraction coupled with
the determination of cobalt in environmental
samples, Anal. Lett., 54 (2021) 378–393.
[26] S. Keshipour, K. Adak, Magnetic d‐
penicillamine‐functionalized cellulose as
a new heterogeneous support for cobalt
(II) in green oxidation of ethylbenzene to
acetophenone. Appl. Org. Chem., 31(2017) e
3774. https://doi.org/10.1002/aoc.3774
Anal. Methods Environ. Chem. J. 4 (3) (2021) 33-46
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Developing a magnetic nanocomposite adsorbent based on
carbon quantum dots prepared from Pomegranate peel for the
removal of Pb(II) and Cd(II) ions from aqueous solution
Hamideh Asadollahzadeh
a,*
, Mahdiyeh Ghazizadeh
a
and Mohammad Manzari
a
a
Department of Chemistry, Faculty of Science, Kerman branch,
Islamic Azad University, Kerman, Iran, P. O. Box 7635131167, Kerman, Iran
ABSTRACT
Agriculture waste is a good choice for the production of carbon dots
owing to its abundance, wide availability, eco-friendly nature. In this
study a novel magnetic bioadsorbent based on carbon quantum dots
(Fe
3
O
4
-PPCQDs) from Pomegranate peel (PP) was used as adsorbent
to remove lead (Pb) and cadmium (Cd) from 50 mL of water and
wastewater samples by magnetic solid phase extraction (MSPE). After
adsorption ions with Fe
3
O
4
-PPCQDs at pH=6, the concentration of
spectrometry (F-AAS). The manufactured of Fe
3
O
4
-PPCQDs and GO
nanostructures were structurally characterized by scanning electron
microscopy (SEM), transmission electron microscopy (TEM), X-ray
diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR).
The quantum dots were optically characterized by UV–Vis spectroscopy.
Batch adsorption experiment was conducted to examine the effects of
pH, contact time, temperature and initial concentration of Pb(II) and
Cd(II) from the water. The preconcentration factor and LOD for Cd
-1
-1
),
respectively. The
equilibrium data of ions sorption were well described by Langmuir and
Freundlich model. The R
2
values obtained by Langmuir model were
higher. The absorption capacity of Fe
3
O
4
-PPCQDs for cadmium and
lead were obtained 17.92 and 23.75 mg g
-1
, respectively.
Keywords:
Carbon quantum dots,
Iron oxide nanoparticles,
Adsorption,
Lead and Cadmium,
Isotherms,
Flame atomic absorption spectrometry
ARTICLE INFO:
Received 2 Jun 2021
Revised form 5 Aug 2021
Accepted 27 Aug 2021
Available online 29 Sep 2021
*Corresponding Author: Hamideh Asadollahzadeh
Email: asadollahzadeh90@yahoo.com
https://doi.org/10.24200/amecj.v4.i03.149
------------------------
1. Introduction
Environmental pollution based on the organic
chemical compounds (VOCs) and heavy metals
(M) have needed a serious threat due to the rapid
development of the chemical industry and the toxic
effect in environment. The contamination of heavy
metals in water through the industrial wastewater is
the global environmental problems [1]. The heavy
metals compounds cannot be decomposed naturally
and cause the various health problems in the living
organism and human. Recently, the elimination of
a result of their persistence into the atmosphere
[2]. Among of heavy metals, cadmium and lead
(Cd and Pb) can be discharged from the several
environment from the steel production, the cement
manufacture, the Ni-Cd battery manufacture,
cadmium electroplating, the phosphate fertilizers
etc. [3]. Bivalent cadmium causes a number
of deformities and diseases in humans, such
as the muscle cramps, the lung problems, the
34
Anal. Methods Environ. Chem. J. 4 (3) (2021) 33-46
kidney degradation, the proteinuria, the skeletal
deformation [4]. On the other hand, common
anthropogenic causes of lead contamination in
groundwater include the smelting, the mining, the
consumption of fossil fuels and the incinerating
solid waste [5]. Lead can cause a cognitive
dysfunction in children, high blood pressure, the
illnesses of the immune system and the reproductive
system [6]. Numerous techniques have been used
to reduce the harmful effects of cadmium and lead
on water source, including the chemical oxidation
and the reduction, the chemical precipitation, the
ion exchange, the electrochemical processes, and
[7]. The performance and
any selectivity. However, among these methods,
[8]. Adsorption
is a mass transfer process where a substance is
transferred from the liquid phase to the surface of
the solid through physical or chemical interaction.
Many kinds of adsorbents, including the activated
carbon [9], the inorganic minerals [10], the biomass
adsorbents [11-13], and polymer [14–17] are used
to remove the metal ions from the liquid phased
such as water and wastewater. By-products from
agriculture feed have always considered due to its
availability and the cost features. Moreover, the
other important characteristics are biocompatibility,
biodegradability and the renewable [18]. Thus
there is an interest in use of agricultural wastes
as a source for preparation of carbon based
nanomaterial. Carbon based quantum dots are
new class of carbon nanomaterials that have been
explored due to their excellent properties [19].
However, the separation of adsorbents, obtained
from agricultural waste, required a high-speed
[20]. Iron oxide has excellent magnetic properties,
the high biocompatibility, easy separation
comparatively low cost. The magnetic iron oxide
with the highest adsorption rates [21]. The surface
oxide using the coating technique improves their
sorption capacity because, the surface coating
phenomenon helps to converting the closely -
packed cubic geometry of magnetic nanoparticles
into compact [22].
Pomegranate peel (PP), as a by-product of the
pomegranate juice industry is an inexpensive
material. It is composed of several constituents,
including polyphenols, ellagic tannin and ellagic
acids [23]. So far, no study has been done on surface
dots prepared from pomegranate peel for developing
magnetic nanocomposite (Fe
3
O
4
-PPCQDs).
The PPCQDs adsorbent has generated from the
pomegranate peel and functionalized with Fe
3
O
4
as
magnetic nanostructure which was used for removing
toxic ions from wastewater. Another advantage is
that the loaded adsorbents could be easily separated
from the aqueous solution using magnet instead of
centrifugation thus conserving energy. In this study,
the material preparation, the characterization and
the batch-type removal experiments were carried
out wherein the feasibility of the above described
composite for the removal of heavy metals Cd(II)
and Pb(II) from aqueous solution which were
investigated by varying the process conditions.
2. Material and Methods
2.1. Apparatus
The concentration of heavy metals (Pb and Cd) in
atomic absorption spectrometry (F-AAS, Model
AAnalyst 800, Air acetylene, Perkin Elmer, USA).
The wavelength of 217.0 nm (Slit :1, Current lamp:
5mA) and 228.8 nm (Slit: 0.5, Current lamp: 3 mA)
was used for lead and cadmium determination,
respectively. The working ranges for lead and
cadmium were achieved 2.5-20 mg L
-1
and 0.2-1.8
mg L
-1
, respectively by sensitivity of 0.06 mg L
-1
.
The LOD of F-AAS for lead and cadmium was
achieved 0.1 mg L
-1
and 0.05 mg L
-1
, respectively.
The auto-sampler from 0.5 to 5 mL was used
for sample introduction to F-AAS. The pH was
measured by electronic pH meter (Benchtop meter
inoLab pH 7110 model, WTW company, Germany).
35
Removal of Pb(II) and Cd(II) by Fe
3
O
4
-PPCQDs Hamideh Asadollahzadeh et al
2.2. Chemicals
Pomegranate peel were obtained from Mahan,
Kerman, Iran. Sodium hydroxide (NaOH),
cadmium nitrate tetrahydrate (Cd(NO
3
)
2
·4H
2
O),
lead nitrate (Pb(NO
3
)
2
), the ferric chloride
hexahydrate (FeCl
3
·6H
2
O), the ferric sulfate
heptahydrate (FeSO
4
.7H
2
O) hydrochloric acid
(HCl) with a purity of 37%, nitric acid (HNO
3
) with
purity 63% was purchased from Merck and all the
chemical reagents were analytical grade. All the
aqueous solutions were prepared by using double
distilled water. The pH of the solution was adjusted
and measured using electronic pH meter. The pH
of the solution was adjusted by adding 0. 1M HCl
or 0. 1M NaOH and measured using electronic pH
meter (Benchtop meter inoLab pH 7110 model,
WTW company, Germany).
2.3. Synthesis of Magnetic Carbon Quantum
Dots (Fe
3
O
4
-CQDs)
The pomegranate peel (PP) has carbon structure
which was ground after washed/ dried in the oven
100
o
C. The ground powder is sifted by small mesh
to obtained for used for synthesis of CQDs. First of
all, 100 grams of ground powder of the pomegranate
peel (PP) mixed with 8 Liters of DW in the 500
mL closed container. The closed container adjusted
and then the temperature decreased (cooling) up
to room temperature for one day. The sediments
the vacuum pump and the black brown product is
created. After UV irradiation (400 nm), the color
of product change into blue photoluminescence
which was showed that a quantum dot particles
synthesized correctly. The CQDs cab be absorbed
the UV irradiation at 220 nm spectrophotometer.
powder. The powder put in the oven based on quartz
type, N
2
powder was carbonized and impurities get out of
oven. After synthesis PPCQDs, the absorption of
by UV peak by spectrophotometer (Fig.1a). the
magnetic Fe
3
O
4
-PPCQDs were prepared by co-
precipitation of FeCl
2
·4H
2
O and FeCl
3
·6H
2
O,
in the presence of PPCQDs [24]. To prepare the
nano magnetic PPCQDs, 10 mg of PPCQDs in
10 mL of DW was ultra-sonicated for I h. To the
resulting mixture was added 12.5 mL solution of
FeCl
2
·4H
2
O (125 mg) and FeCl
3
·6H
2
O (200 mg)
in deionized water (10 mL) at room temperature.
Then, 30% ammonia solution was added for the pH
= 11 and the temperature was increased to 60
C.
After being stirred for 1 h, the product was cooled at
25
o
3
O
4
-PPCQDs
centrifuged at 4000 rpm for 20 min, washed and
dried at 75
o
C (Fig.1 b).
Fig.1. a) UV absorption by CQDs product b) The
mechanism of synthesis of Fe
3
O
4
-PPCQDs
36
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-46
2.4. Batch mode adsorption and analytical
procedure
Adsorption of Pb(II) and Cd(II) based on Fe
3
O
4
-
PPCQDs adsorbent was achieved in optimized
experimental conditions such as pH, the contact
time, the amount of adsorbent and temperature. The
experiments were carried out in 50 ml Erlenmeyer
from pH 2 to 8, the sample volume of 50 mL, the
contact time between 2 - 60 minute, the amount
of biosorbent from 0.01 to 0.2 g, the temperature
between 5-45
o
C and the concentration of ions
5-150 mg L
-1
. To adjust required The pH of aqueous
solution was adjusted with HCl (0.1 M) and NaOH
(0.1 M). Finally, the thermodynamic parameters and
isotherms were studied. The Fe
3
O
4
-PPCQDs were
of remaining Pb(II) and Cd(II) in water by F-AAS
after back extraction solid phase by 1 mL mixture
of HNO
3
0.1 M/DW. Moreover, the linear ranges
of MSPE procedure for cadmium and lead based
on Fe
3
O
4
-1
and
-1
, respectively (RSD%<2.4). So, the
trace analysis of lead and cadmium (sub-ppb) can
be created by the Fe
3
O
4
-PPCQDs adsorbent. The
quantity of adsorbed ion per unit mass of biosorbent
was calculated from Equation 1:
q
e
= (C
0
-C
e
) × V/m (1)
where C
o
and C
e
are the concentrations of Pb(II)
and Cd(II) at the beginning and at the end of the
adsorption process.
3. Result and discussion
3.1. Characterization
X-ray diffraction (XRD) patterns were recorded
on a Seifert TT 3000 diffractometer (Ahrensburg,
of the sorbents were calculated by the Brunauer-
Emmett-Teller (BET) and Barrett-Joyner-Halenda
(BJH) methods, respectively. Scanning electron
microscopy (SEM, Phillips, Netherland) was used
for surface image of the CQDs The morphology
of sorbent was examined by transmission electron
microscopy (TEM, Philips, Netherland). The Fourier
transform infrared spectrophotometer (FTIR, Bruker
GmbH, Germany) using KBr pelleting method was
used in the 4000–200 cm
3.2. Fourier-transform infrared spectroscopy (FTIR)
The FTIR spectra of Fe
3
O
4
-PPCQDs adsorbent are
shown in Figure 2. The prime spectrum of FTIR
of CQDs is shown in black line as nonactivated
form (Fig. 2a) and red line (activated/HNO
3
)
which has different wavenumbers but both of them
-
1
,1200 cm
-1
,1250 cm
-1
belong to C-O bond and
the peak of 1381 cm
-1
shows the formation of C-H
bond. Additionally a peak of 1585 cm
-1
is observed
for C=C bond and the another peak appeared in
Fig.2(a). The spectrum of FTIR of CQDs
37
Removal of Pb(II) and Cd(II) by Fe
3
O
4
-PPCQDs Hamideh Asadollahzadeh et al
3300 cm
-1
shows the O-H bond. In Figure 2 (b),
the red graph is the sample activated with nitric
acid vapour. Meanwhile similar peaks of 3340
cm
-1
(O-H bond) were observed in Figure 2(a,b).
In addiition FTIR of Fe
3
O
4
-PPCQDs was shown
in Figure 2 C which has a peak in 582 cm
-1
belong
to Fe
3
O
4.
3.3. XRD spectra of CQD
In Figure 3, the X-ray diagram was shown for
carbon quantum dots(CQDs) and magnetic
carbon quantum dots (Fe
3
O
4
-PPCQDs). The
XRD curve of Fe
3
O
4
-PPCQDs is similar to simple
form of CQDs. In this pattern two main Peaks
were observed. The observed wide peak is in the
intensity of 24 degrees in page (002) relates to
the graphite. The width peak can have related to
mall size of carbon quantum dots. The observed
Fe
3
O
4
-PPCQDs peak in 45 degree angle relate
to (101) which indicates similar to graphene
formed by quantum dot particles. The XRD
pattern for CQDs is similar to Fe
3
O
4
-PPCQDs
which was indicated that carbon quantum dots
modified with PP and Fe
3
O
4
did not changed on
the structural order of CQDs.
Fig.2(b). The spectrum of FTIR of HNO
3
-CQDs
Fig.2(c). The spectrum of FTIR of Fe
3
O
4
-PPCQDs
38
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-46
3.4. Field emission scanning electron
microscope (FE-SEM)
The surface morphology of the CQDs was reported
SEM). The FE-SEM of CQDs have been shown
in Figure 4(a). The CQDs primary samples were
formed as blocks of nano particles carbon. The
blocks are as a colony and forms big volume of
CQDs. The smallest size the structure was between
10 to 30 nanometer which consists of very small
particles of CQDs. The FE-SEM of the Fe
3
O
4
-
PPCQDs was shown in Figure 4(b) with size of 10-
25 nm.
3.5. Transmission electron microscopy (TEM)
Transmission electron microscopy (TEM) was used
to study of the nanostructure size. The microscopic
pictures of the CQDs have been shown in Figure 5a.
which the carbon particles are so small. Moreover,
the formation of Fe
3
O
4
-PPCQDs has very small
particles which is clearly visible by TEM (Fig.5b).
3.6. Bach adsorption studies
3.6.1. pH dependent studies
The effect of pH (Fig. 6a and b) on the adsorption of
Pb(II) and Cd(II) ions was studied by Fe
3
O
4
-PPCQDs.
Fig.3. The XRD diagram of CQDs and Fe
3
O
4
-PPCQDs
Fig.4a. The FESEM of CQDs Fig.4b. The FESEM of Fe
3
O
4
-CQDs
39
Removal of Pb(II) and Cd(II) by Fe
3
O
4
-PPCQDs Hamideh Asadollahzadeh et al
In order to determine the optimum pH, the pH range
between 2.0–11.0 was evaluated for Pb(II) and Cd(II)
ions. While screening the pH values, all the other
process variables were kept constant. A control
experiment was also run (in the absence of Fe
3
O
4
-
PPCQDs) for the removal Pb(II) and Cd(II) to
explore the effect of chemical precipitation (Fig. 6a).
The control experiment revealed that there was no
removal of Pb(II) and Cd(II) up to pH 7.0 but when
the pH was more than 7.0 both ions precipitated
as hydroxides [Pb(OH)
2
and Cd(OH)
2
] in the
solution thus, leading to their complete removal
without Fe
3
O
4
-PPCQDs. Also, the adsorption of
Fe
3
O
4
-PPCQDs was shown in Figure 6b. Due to
interaction of ions with adsorbent, the maximum
removal for Pb(II) and Cd(II) was achieved at
pH 6.0. The adsorption of Pb(II) and Cd(II) was
decreased at lower and upper pH of 6 (5.5>pH>6.5).
This behavior may be due to the reason that: lower
pH leads to an abundance of hydronium ions (H
3
O
+
)
in the solution that causes competition between
hydronium ions and Pb(II) and Cd(II) ions for
adsorption onto Fe
3
O
4
-PPCQDs. Thereby lowering
occurred at lower pH [25]. On the other hand, by
increasing pH, the adsorption also increased, which
can be showed that in this range (neutral and weakly
acidic) most metals are available as soluble and free
cations for adsorption. One of the important factors
related to the chemical structure of the adsorbent is
the point – zero charge pH (pH
pzc
). At this pH, there
is no charge on the surface.
Fig.5a. The TEM of CQDs Fig.5b. The TEM of Fe
3
O
4
-PPCQDs
Fig.6. a) Effect of pH on Pb(II) and Cd(II) removal without Fe
3
O
4
-PPCQDs, b) with Fe
3
O
4
-PPCQDs adsorbent
40
3.6.2. Effect of time
The effect of contact time on the removal
of Pb(II) and Cd(II) by Fe
3
O
4
-PPCQDs was
investigated to determine the optimum time
taken to attain the equilibrium. The adsorption
experiments were carried out by varying the
contact time between 2 and 60 min, keeping all
other process variables constant. Figure 7 depicts
that the removal percentage was increased by
increasing of the contact time. The equilibrium
was achieved for 20 min and after this time,
the further removal for Pb(II) and Cd(II) ions
was not observed (constant). It was observed
that, the rate of adsorption of ions was faster at
initial stages, that this may be attributed to the
quick uptake of ions onto the large surface area
of Fe
3
O
4
-PPCQDs up to 20 min and after it the
adsorption progress was slowly followed and
remained constant.
Fig. 7. Effect of contact time on Pb(II) and Cd(II)
removal by Fe
3
O
4
-PPCQDs
3.6.3. Effect of amount of adsorbent
The effect of amount of Fe
3
O
4
-PPCQDs was
investigated under optimized conditions (pH=6
and contact time: 20 min.). As shown in Figure 8,
the adsorption increased with the Fe
3
O
4
-PPCQDs
amount up to 0.1 g. Also, the adsorbent surface
has saturated with the extra value of Pb(II) and
Cd(II) ions in optimized mass. At higher amount
of adsorbent, the adsorption yield is almost
unchanged, because the most of Pb(II) and Cd(II)
ions interact with Fe
3
O
4
-PPCQDs surface.
Fig. 8. The effect of adsorbent amount on Pb(II) and
Cd(II) removal Fe
3
O
4
-PPCQDs
3.6.4. Effect of temperature
The effect of the temperature on adsorption of
Pb(II) and Cd(II) ions was examined. As shown
in Figure 9, the adsorption was reduced as the
temperature rising (
of metal ions on Fe
3
O
4
-PPCQDs was exothermic
process and by increasing temperature the removal
Pb(II) and Cd(II) ions on Fe
3
O
4
-PPCQDs adsorbent
depended on the low temperature.
Fig. 9. The effect of temperature on Pb(II) and Cd(II)
removal by the Fe
3
O
4
-PPCQDs
3.6.5. Effect of initial concentration of Cd(II)
and Pb(II)
The effect of initial concentrations of Pb(II) and Cd(II)
on adsorption process based on Fe
3
O
4
-PPCQDs were
evaluated at various concentration from 10 to 150
mg L
. In addition, the all of other parameters are
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-46
41
constant which is shown in Figure 10a. The Figure
10a revealed that the metal removal was reduced by
the Fe
3
O
4
-PPCQDs when the metal concentration
increased from 10 to 150 mg L
in the solution. The
decreased for Cd(II) and Pb(II) from 88.60 to 44 and
94.61 to 55.22, respectively. The reduce of removal
may be due to covering /coating of the most surface
sites of Fe
3
O
4
-PPCQDs with high concentration of
Pb(II) and Cd(II) and the adsorption capacity of the
adsorbent get exhausted due to non-availability of
free binding sites [25]. Also, at low concentration
ranges, the percentage of adsorption is high because
of the availability of more active sites on the surface
of adsorbent. Figure 10b showed that the adsorption
capacity against ion concentrations. The increase
in adsorption capacity depended on initial metal
concentration which was led to increase the diffusion
of Pb(II) and Cd(II) ions from the liquid phase to the
surface of the solid phase. So, the driving force of
the metal ions cause to lead to the collisions between
metal ions and the nanoparticles surface. Therefore,
the adsorption capacity was increased [23].
3.7. Adsorption thermodynamic
The adsorption process was analyzed by
thermodynamic theory. The thermodynamic
Fe
3
O
4
-PPCQDs were calculated by Equations 2-5
[26]:
(Eq. 2)
(Eq. 3)
(Eq. 4)
(Eq. 5)
where R (8.314 J mol
K
) is the universal
gas constant, K is the equilibrium constant at
temperature T, T is the absolute temperature (K),
Ce (mg L
) is the equilibrium concentration and qe
is the amount of Cd(II) and Pb(II) adsorbed on the
surface of the Fe
3
O
4
-PPCQDs. Figure 11 shows the
and temperature. Table 1
gives the thermodynamic parameters for adsorption
of Cd(II) and Pb(II) adsorbed on the surface of the
Fe
3
O
4
-PPCQDs adsorbent at different temperatures.
As can be seen from the Table 1 the negative
is feasible and spontaneous in nature. With the
shifts to more positive
values indicating that the increase in temperature
Fig. 10. a). Effect of initial metal ion concentration on Pb(II) and Cd(II) removal by Fe
3
O
4
-PPCQDs,
b) adsorption capacity against metal ion concentration.
Removal of Pb(II) and Cd(II) by Fe
3
O
4
-PPCQDs Hamideh Asadollahzadeh et al
42
was not favorable for the adsorption process
[27]
adsorption process is exothermic. That was also the
reason equilibrium adsorption of Cd(II) and Pb(II)
decreased as the rising of solution temperature
K
for adsorption of Cd(II) and
the interface of the Fe
3
O
4
-PpCQDs and solution was
reduced during the adsorption process.
Fig.11 and temperature
3.8. Adsorption isotherms
The most popular isotherms are Langmuir and
Freundlich [28] models. The Langmuir model
describes monolayer adsorption, however
Freundlich model show heterogeneous surface.
The linear form of Langmuir model is given by
following Equation 6:
(Eq. 6)
where C
e
(mg L
-1
) is the equilibrium concentration
of the solution, q
e
(mg g
-1
) is the amount of metal
m
(mg
g
-1
) is the maximum amount of metal ions required
to form monolayer, K (L mg
-1
) is the adsorption
equilibrium constant (Fig. 12). Freundlich
adsorption model demonstrate that adsorbents
have a heterogeneous surface having site with
different adsorption potential. It moreover expects
the binding strength decreases with the increasing
degree of occupation. The Freundlich adsorption
model in its linear form is given in Equation 7:
(Eq. 7)
where K
f
(mg g
) is the Freundlich constant
indicating adsorption capacity, n (L mg
) is the
adsorption intensity that is the measure of the
in adsorption density. The Freundlich constants K
f
and n were calculated from the slope and intercept
of the plot of Ce versus log10 qe (Fig. 13) that
shown in Table 2. The values of Langmuir R
2
for
Cd(II) and Pb(II) by the Fe
3
O
4
-PPCQDs were
higher than Freundlich model thus, indicating that
thereby indicating monolayer adsorption.
Table 1. Thermodynamic parameters for adsorption of Pb(II) and Cd(II) by
Fe
3
O
4
-PPCQDs at different temperatures
Ion T (K) ΔG (J mol
-1
) ΔH (J mol
-1
) ΔS (J mol
-1
) R
2
Pb (II)
278 -8700
-16908 -29.32 0.978
288 -8510
298 -8256
308 -7800
318 -7589
Cd (II)
278 -7105
-10947 -13.93 0.980
288 -6923
298 -6748
308 -6664
318 -6538
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-46
43
3.9. Comparison of adsorption capacity with
other adsorbents
The maximum adsorption capacity of Fe
3
O
4
-PPCQDs
nanocomposite for the removal of Pb(II) and Cd(II)
was compared with other adsorbents reported in the
literature and the values are given in Table 3. It is clear
from Table 3, that the adsorption capacity of Fe
3
O
4
-
PPCQDs. is comparable with other nanomaterials
suggesting that, it is effective in removing Pb(II) and
Cd(II) from aqueous solutions [29-33].
Table 2. Langmuir and Freundlich isotherm parameters for the removal of Pb(II) and Cd(II)
by the Fe
3
O
4
-PPCQDs
Parameters Pb(II) Cd(II)
Langmuir parameters
q
m
(mg g
-1
)
b (L mg
-1
)
R
2
23.75
0.120
0.9842
17.92
0.092
0.9815
Freundlich Parameters
K
f
(mg g
-1
)
n (L mg
-1
)
R
2
3.82
2.22
0.9748
2.5
2.21
0.965
Fig. 12. Linear Langmuir isotherm for Pb(II)
and Cd(II) removal by the Fe
3
O
4
-PPCQDs.
Fig. 13. Linear Freundlich isotherm for Pb(II)
and Cd(II) removal by the Fe
3
O
4
-PPCQDs.
Table 3. Comparison of adsorption capacity of the Fe
3
O
4
-PPCQDs with other adsorbents.
Adsorbents
Adsorption capacity (mg g
-1
)
pH
Adsorbent
mass (mg).
Ref.
Cd (II) Pb (II)
CFe
3
O
4
4.106 3.795 3 50 29
PMNPs 29.60 3.103 1 to 8 50 30
Kaniar Fe
3
O
4
2.20 1.35 5 200 31
MCANF ----- 44 6 100 32
Sawdust (Fe3O4/SC) 63 ----- 6.5 400 33
This study 17.92 23.75 6 100 -----
CFe
3
O
4
: Chitosan/iron oxide nanocomposite
Kaniar Fe
3
O
4
: Magnetic Bauhinia purpurea (Kaniar) powders
MCANF: Fe
3
O
4
Removal of Pb(II) and Cd(II) by Fe
3
O
4
-PPCQDs Hamideh Asadollahzadeh et al
44
4. Conclusions
In this article, the adsorption potential of the Fe
3
O
4
-
PPCQDs nanocomposite was investigated for the
removal of Pb(II) and Cd(II) ions. TEM analysis
revealed that the synthesized nanoparticles have
an average particle size of 10-25 nm for the Fe
3
O
4
-
PPCQDs. The XRD analysis of Fe
3
O
4
-PPCQDs
exhibiting average crystal size similar to that
indicated by the TEM analysis. Batch adsorption
experiments were led to study the effect of
various parameters like agitation time, adsorbent
dosage, initial concentration of the Pb(II) and
Cd(II), temperature, and pH. The conditions for
nanocomposite for the removal of Pb(II) and
Cd(II) were achieved (pH=6.0, temperature=25
contact time =20 min). Based on procedure, the
maximum Langmuir adsorption capacity was
obtained 17.92 mg g
for Cd(II) and 23.75 mg
g
for Pb(II) at pH 6. In addition, the working
ranges of cadmium and lead adsorption based on
Fe
3
O
4
-PPCQDs nanocomposite in 50 mL of water
-1
L
-1
, respectively by the MSPE procedure (PF=50,
RSD%<2.4). Therefore, the ultra- trace analysis
of Pb(II) and Cd(II) ions was done by Fe
3
O
4
-
PPCQDs nanocomposite at pH=6.
5. Acknowledgments
The authors would like to thank from Department
of Chemistry, Kerman Branch, Islamic Azad
University, Kerman, Iran.
6. References
[1] A. T. Jan, M. Azam, K. Siddiqui, A.A.I.
Choi, Q.M.R. Haq, Heavy metals and human
health: mechanistic insight into toxicity and
counter defense system of antioxidants. Int.
J. Mol. Sci., 16 (2015) 29592–29630.
[2] R. Singh, N. Gautam, A. Mishra, R. Gupta,
Heavy metals and living systems: an
overview. Indian J. Pharmacol ., 43 (2011)
246-253.
[3] W. Shotyk, G.L. Roux, A. Sigel, H. Sigel,
R.K.O. Sigel, Metal ions in biological
systems, Taylor and Francis, Boca Raton,
Chapter 10, 2005.
[4] M.A.A. Zaini, R. Okayama, M. Machida,
Adsorption of aqueous metal ions on cattle-
manure compost based activated carbons, J.
Hazard. Mater., 170 (2009) 1119-1124.
R. A. Cuevas-Villanueva, E. M. Rivera-
Muñoz, R. Huirache-Acuña, Cd(II) and
Pb(II) adsorption using a composite
obtained from Moringa oleifera Lam,
nanoparticles, Water, 13 (2021) 89.
[6] W. Zhang, X. Shi, Y. Zhang, W. Gu, B.
Li, Synthesis of water-soluble magnetic
graphene nanocomposites for recyclable
removal of heavy metal ions, J. Mater.
Chem. A, 1 (2013) 1745-1753.
[7] H. Isawi, Using zeolite/polyvinyl alcohol/
sodium alginate nanocomposite beads
for removal of some heavy metals from
wastewater, Arab. J. Chem., 13 (2020)
5691-5716.
[8] R. Ahmad, A. Mirza, Facile one pot green
synthesis of chitosan-iron oxide (CS-Fe
2
O
3
)
nanocomposite: removal of Pb(II) and Cd(II)
from synthetic and industrial wastewater, J.
Clean. Prod., 186 (2018) 342-352.
[9] H. C. Tao, H. R. Zhang, J. B. Li, W. Y.
Ding, Biomass based activated carbon
obtained from sludge and sugarcane bagasse
for removing lead ion from wastewater,
Bioresour. Technol., 192 (2015) 611-617.
[10] M. F. Gao, Q. L. Ma, Q.W. Lin, J. L. Chang,
H. Z. Ma, A novel approach to extract SiO
2
properties, Mater. Design., 116 (2017) 666–
675.
[11] Y. K. Tang, L. Chen, X. R. Wei, Q. Y. Yao,
T. Li, Removal of lead ions from aqueous
solution by the dried aquatic plant, Lemna
perpusilla Torr, J. Hazard. Mater., 244
(2013) 603-612.
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-46
45
by click reaction for selective extraction of
noble metal ions, Bioresour. Technol., 177
(2015) 182-187.
[13] T. M. Abdel-Fattah, M. E. Mahmoud, S. B.
Ahmed. Biochar from woody biomass for
removing metal contaminants and carbon
sequestration, J. Ind. Eng. Chem., 22 (2015)
103-109.
[14] S. Haider, F.A.A. Ali, A. Haider, W. A. Al-
Masry, Y. Al-Zeghayer, Novel route for amine
membrane for the removal of copper and
lead ions from aqueous medium, Carbohydr.
Polym., 199 (2018) 406-414.
[15] Q. Feng, D. Wu, Y. Zhao, A. Wei, Q. Wei,
H. Fong, Electrospun AOPAN/RC blend
of heavy metal ions from water, J. Hazard.
Mater., 344 (2018) 819–828.
[16] Q. Lv, X. Hu, X. Zhang, L. Huang, Z. Liu, G.
ions by using poly (acrylic acid) hydrogel
adsorbent, Mater. Design., 181 (2019)
107934.
[17] F. Arshad, M. Selvaraj, J. Zain, F. Banat,
graphene oxide hydrogel composite as an
Purif. Technol., 209 (2019) 870-880.
[18] R. Song, M. Murphy, C. Li, K. Ting, C.
Soo, Z. Zheng, Current development of
biodegradable polymeric materials for
biomedical applications, Drug Des. Devel.
Ther., 24 (2018) 3117-3145.
[19] H. Baweja, K. Jeet, Economical and green
synthesis of graphene and carbon quantum
dots from agricultural waste, Mater. Res.
Express, 6 (2019) 0850g8.
[20] M. M. Rhaman, M. R. Karim, M. K.
Mohammad Ziaul, Y. Ahmed, Removal of
bioadsorbent based on Jute Stick powder
and its adsorption isotherm, kinetics and
regeneration study, Water Air Soil Pollut.,
231 (2020) 1-18.
[21] P.N. Dave, L.V. Chopda, Application of
iron oxide nanomaterials for the removal
of heavy metals, J. Nanotechnol., 4 (2014)
1-14
[22] M.O. Ojemaye, O.O. Okoh, A.I. Okoh,
from wastewater, progress and prospects,
Mater. Express, 7 (2017) 439-456.
[23] B. R. Seeram, M. Lee, D. Heber, Rabid
pomegranate husk, Sep. Puri. Technol., 41
(2005) 49-55.
[24] H. Wang, X. Xu, Z. Ren, B. Gao, Removal
of phosphate and chromium(VI) from
liquids by an aminecrosslinked nano-Fe
3
O
4
biosorbent derived from corn straw, RSC
Adv., 6 (2016) 47237-47248.
[25] M. Jain, M Yadav, T. Kohout, M. Lahtinen,
V.K. Garg, Development of iron oxide/
activated carbon nanoparticle composite for
the removal of Cr(VI), Cu(II) and Cd(II)
ions from aqueous solution, Water Resour.
Ind., 20 (2018) 54-74
[26] M.I. Panayotova, Kinetics and
thermodynamics of copper ions removal
from wastewater by use of zeolite, Waste
Manag., 21 (2001) 671-676.
[27] L. Xu, X. Zheng, H. Cui, Z. Zhu, J.
Liang, J. Zhou, Equilibrium, kinetic, and
thermodynamic studies on the adsorption
of cadmium from aqueous solution by
Appl., 2017 (2017) 1-9. https://doi.
org/10.1155/2017/3695604
[28] H. Zare, H. Heydarzadeh, M. Rahimnejad,
Dried activated sludge as an appropriate
biosorbent for removal of copper (II) ions,
Arab. J. Chem., 8 (2015) 858-864.
[29] M. Keshvardoostchokami, L. Babaei,
A. A. Zamani, A. H. Parizanganeh, F.
Piri, Synthesized chitosan/iron oxide
nanocomposite and shrimp shell in removal
Removal of Pb(II) and Cd(II) by Fe
3
O
4
-PPCQDs Hamideh Asadollahzadeh et al
46
of nickel, cadmium and lead from aqueous
solution, Global J. Environ. Sci. Manag., 3
(2017) 267–278.
[30] F. Ge, M. Li, H. Ye, B. Zhao, Effective removal
of heavy metal ions Cd
2+
, Zn
2+
, Pb2+, Cu
2+
magnetic nanoparticles, J. Hazard. Mater.,
211 (2012) 366–372.
[31] R. Sharma, A. Sarswat, C.U. Pittman, D.
Mohan, Cadmium and lead remediation
using magnetic and non-magnetic sustainable
biosorbents derived from bauhinia Purpurea
Pods, RSC Adv., 7 (2017) 8606–8624.
[32] T. I. Shalaby, M.F. El-Kady, A.E.H.M. Zaki,
S. M. El-Kholy. Preparation and application
of magnetite nanoparticles immobilized on
from polluted water, Water Supply, 17 (2017)
176–187.
[33] N. Kataria, V. K. Garg, Green synthesis of
Fe
3
O
4
nanoparticles loaded sawdust carbon
for cadmium (II) removal from water:
regeneration and mechanism, Chemosphere,
208 (2018) 818–828.
Anal. Methods Environ. Chem. J. 4 (3) (2021) 21-46
1. Introduction
The sixteen polycyclic aromatic hydrocarbons
(PAHs) in the United States environmental
protection agency and European community (US,
EPA) are considered as priority pollutants [1, 2]
The
PAHs are toxic organic contaminants with great
environmental and health concern, which consist of
two or more fused aromatic rings. PAHs containing
up to two fused benzene rings such as anthracene
and phenanthrene are known as light PAHs and
those containing more than four benzene rings
such as ovalene and corannulene are called heavy
PAHs[3]. The main source of PAHs contamination
is incomplete combustion and pyrolysis of wood
or fossil fuels, the motor oil and petroleum spill
which are disposed of improperly each year into
soil[4]. Owing to the persistence of PAHs in soil
Anal. Methods Environ. Chem. J. 4 (3) (2021) 47-58
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
A novel modied fenton-like process for efcient
remediation of anthracene-contaminated soils before
analysis by ultraviolet–visible spectroscopy
Mahdia Hamidinasab
a,b,*
, Mohammad Ali Bodaghifard
a,b
, Sepideh Ahmadi
b
, Ali Seif
a
and Zahra Najahi Mohammadizadeh
a
a
Department of Chemistry, Faculty of Science, Arak University, Arak 88138-38156, Iran.
b
Institute of Nanosciences and Nanotechnology, Arak University, Arak 88138-38156, Iran.
ABSTRACT
Due to the persistence of polycyclic aromatic hydrocarbons (PAHs)
in soil and sediments, and their toxic, mutagenic, and carcinogenic
effects, the remediation of PAH-contaminated sites is an important
role for environment pollution. In this study, the chemical oxidative
remediation of anthracene-contaminated soils was investigated by
magnetite nanoparticles (Fe
3
O
4
) catalyzed Fenton-like oxidation in
the presence of hydrogen peroxide 30% (H
2
O
2
) and urea-hydrogen
peroxide (UHP) at neutral pH. Urea-hydrogen peroxide (UHP), as a
The magnetite nanoparticles improved the production of hydroxyl
radicals, and the removal of polycyclic aromatic hydrocarbons
(anthracene as a model compound) from the soil samples. The
structure of Fe
3
O
4
nanoparticles was characterized by Fourier-
transform infrared spectroscopy (FT-IR), X-ray powder diffraction
(XRD), scanning electron microscopy (SEM), and vibrating sample
initial concentration 2500 (mg kg
-1
) was 95% for 2.5 mmol by using
hydrogen peroxide and 93% for 0.1 mmol of UHP at the optimum
oxidation condition. The anthracene reaction was analyzed by
ultraviolet-visible spectroscopy (UV-Vis). The UHP safety and
magnetic separation makes magnetite nanoparticles-UHP a promising
catalytic system in remediation of polycyclic aromatic hydrocarbons
in contaminated soils.
Keywords:
Polycyclic aromatic hydrocarbon (PAH),
reaction,
Magnetite nanoparticle,
Urea-hydrogen peroxide (UHP)
ARTICLE INFO:
Received 20 May 2021
Revised form 30 Jul 2021
Accepted 17 Aug 2021
Available online 30 Sep 2021
*Corresponding Author: Mahdia Hamidinasab
Email: mahdiahamidinasab@yahoo.com
https://doi.org/10.24200/amecj.v4.i03.140
------------------------
48
and sediments, and their toxic, mutagenic, and
carcinogenic effects, the remediation of PAH-
contaminated sites is an important environmental
issue. Various remediation techniques including
incineration, thermal conduction, solvent
extraction/soil washing, chemical oxidation, bio-
augmentation, bio-stimulation, phytoremediation,
composting/bio-piles and bioreactors have been
explored and studied for the removal of persistent
PAHs from complex matrices like soil or sediments.
Integrating physico-chemical and biological
technologies is also widely practiced for better
clean-up of PAH contaminated soils. Electrokinetic
remediation, vermiremediation and biocatalyst
assisted remediation are at the development stage[5]
In situ chemical oxidation (ISCO) has emerged as
a cost-effective and viable remediation technology
for the treatment of several pollutants in ground
waters, soils and sediments[6–8]. Remediation by
chemical oxidation involves the injection of strong
oxidants such as hydrogen peroxide[9], ozone
gas[10], potassium permanganate[11], etc. In last
two decades a lot of researches have been addressed
to this aim and pointed out the prominent role of
as advanced oxidation processes (AOPs), which
usually operated at or near ambient temperature and
pressure[12, 13]. Advanced oxidation processes
because of their effective and rapid degradation
performance, including photocatalysis [4, 14, 15],
ozonisation[16], electrochemical reactions[17]
and Fenton method[18, 19]. Among chemical
oxidation processes, special attention has been paid
to the use of Fenton’s reagent, which release the
hydroxyl radicals with high oxidation potential
(E
=2.73 V), from the catalytic decomposition of
H
2
O
2
in the presence of Fe (II) or Fe (III) ions. The
Fenton method has the ability to oxidize a wide
range of organic pollutants and convert them to
CO
2
, H
2
O and inorganic compounds or, at least,
transform them into harmless or biodegradable
products[20–23].
This conventional Fenton’s
process is limited by the optimum pH (~3), such
as at low pH results in negative impacts on soil
properties and is incompatible with subsequent
biodegradation. In the novel process as known as
Fenton-like oxidation, the iron minerals or organic
chelating agents can be applied to extend its range
of applicability at circumneutral soil pH. The
degradation of PAHs has been reported by Fenton-
like reaction catalyzed by various Fe (III) oxides
like ferrihydrite, hematite or goethite[24–26].
Recently, Fe(II) bearing minerals such as magnetite
(Fe
3
O
4
) were found to be the most effective
nanocatalyst as compared to the only Fe(III)
oxides for heterogeneous catalytic oxidation of
organic pollutants[26-29]. The researchers must
be very careful when dispensing oxidizers from
storage containers, avoid spilling material and
contaminating their skin or clothing which can
cause serious accidents. Urea-hydrogen peroxide
(UHP) contains solid and water-free hydrogen
peroxide, which offers a higher stability and better
controllability than liquid hydrogen peroxide
when used as an oxidizing agent. Urea-hydrogen
peroxide adducts (UHP) is stable, inexpensive and
an easily handled reagent. So, the UHP is used as a
organic molecules.
In this study, the anthracene as a model polycyclic
aromatic hydrocarbon was removed from
using hydrogen peroxide and urea-hydrogen
peroxide separately in the presence of bare
magnetite nanoparticles (Fe
3
O
4
) as a nanocatalyst
at circumneutral soil pH.
2. Experimental
2.1. Materials and apparatus
Anthracene 96% (CAS 120-12-7) and H
2
O
2
30%
(CAS 7722-84-1) were used as a contaminant and
oxidant respectively. Ethanol 99.7% (CAS 64-
17-5), Iron (II) chloride tetra hydrate 99% (CAS
13478-10-9) and Iron (III) chloride hexahydrate
98% (CAS 10025-77-1) were purchased from
Merck Company. All reagents were used without
recorded on Bruker Alpha spectrophotometer in the
region 400-4000 cm
-1
using pressed KBr discs. The
Anal. Methods Environ. Chem. J. 4 (3) (2021) 47-58
49
SEM) was carried out by a MIRA III TESCAN-
XMU. The hysteresis loop was measured at
room temperature using a vibrating sample
magnetometer (Model 7300 VSM system, Lake
Shore Cryotronic, Inc., Westerville, OH, USA).
The UV-Vis spectrophotometer (Agilent 8453) was
used to determine the oxidation process.
2.2. Soil Samples
Crushing and preparing of the samples was
performed at geology department of Kharazmi
University (Iran, Tehran) and powdering was done
at the Iranian mineral processing research center
(IMPRC). The analysis of whole-rock major and
trace elements was conducted at ETH, Zurich. The
major elements are summarized in Table 1.
2.3. Preparation of Fe
3
O
4
nanoparticles
Magnetite nanoparticles (MNPs) was synthesized
by co-precipitation method [31]. Aqueous solutions
of FeCl
3
.6H
2
O (56 mmol) and FeCl
2
.4H
2
O (28
mmol) were prepared in de-ionized water (25 mL)
and NaOH (3 M) solution was added to it slowly
and stirred continuously using a magnetic stirrer to
reach the pH=12. This solution was heated under N
2
DW/ ethanol before dried at 60 ºC (Equation 1).
FeCl
2
.4
H
2
O
+
2FeCl
3
.6
H
2
O
+
8NH
4
OH
N
2
atmosphere
Water,
90
Fe
3
O
4
+
8NH
4
Cl
+
20H
2
O
FeCl
2
.4
H
2
O
+
2FeCl
3
.6
H
2
O
+
8NH
4
OH
N
2
atmosphere
Water,
90
Fe
3
O
4
+
8NH
4
Cl
+
20H
2
O
(Eq. 1)
2.4. Calibration curve
Figure 1 shows the UV-Vis absorption spectra
and calibration curve of anthracene for different
by using the Lambert-Beer’s law (Equation 2) [32].
(Eq. 2)
Anthracene removal from soils by Fe3O4-Fenton process Mahdia Hamidinasab et al
Table 1. Total elemental analyses of soil sample.
Compound SiO
2
TiO
2
Al
2
O
3
Fe
2
O
3
FeO MnO MgO CaO Na
2
O K
2
O P
2
O
3
Wt.% 56.84 0.69 16.84 0.90 5.98 0.11 2.15 6.20 4.38 1.93 0.19
Fig. 1. UV-Vis absorption spectra and calibration curve of anthracene
in the wavelength range 200-400 nm
50
2.5. Preparation of anthracene-contaminated soil
Soil samples was prepared as detailed in the
literature,[33] where an ethanol solution with
approximately 500 mg of anthracene was distributed
and mixed manually onto 20 g of clean soil with a
spatula which was homogenized.
2.6. Procedure od anthracene extraction
All experiments were carried out without pH
adjustment and the experiments were done
on a laboratory scale. All experimental runs
were performed at room temperature. For all
experiments, 1 gr (dry mass) of contaminated soil
sample was placed in the tube, 2 mL of deionized
water (DW) was added, followed by the required
quantities of oxidants (H
2
O
2
and urea- H
2
O
2
)
and magnetite as a nanocatalyst (Table 2). The
samples were shacked for 30 minutes. The residual
anthracene in the soil sample was extracted in 8
mL of ethanol during 10 minutes and controlled
the tube centrifugation for 15 min at 3000 rpm.
The presence of anthracene in the solutions was
analyzed by UV-Vis spectrophotometer (
max
=250
nm). Figure 2 illustrates the oxidation process of
quantify decomposition of anthracene in soil was
shown in Equation 3 as follows,
(Eq. 3)
Where X
Anthracene
is the percentage of anthracene
decomposed in soil, C
0
and C
t
are the initial and
3. Result and discussions
3.1. Characterizations
The Fe
3
O
4
nanoparticles were carefully prepared[34]
and characterized by Furrier-transform infrared
spectroscopy (FT-IR), X-ray powder diffraction
(XRD), scanning electron microscopy (SEM),
and vibrating sample magnetometer (VSM).
The X-ray diffraction analysis (XRD) of Fe
3
O
4
nanoparticles shows several diffraction peaks at
74.33 that attributed to the miller planes 220, 311,
400, 422, 511, 440 and 533 respectively (Fig. 3a).
These results are in accordance with the standard
patterns (JCPDS CardNo. 85-1436)[34] The FT-
IR spectra of Fe
3
O
4
MNPs is shown in Figure 3b.
The appeared vibrational frequencies in the 584-
631 cm
-1
region are attributed to the Fe-O bonds.
Anal. Methods Environ. Chem. J. 4 (3) (2021) 47-58
Fig. 2.
51
The stretching frequencies of hydroxyl groups,
on the surface of the nanoparticles, appeared
at 3420 cm
-1
and the peak in the 1625 cm
-1
are
related to the bending vibrations of OH groups.
The morphology and particle size distribution of
Fe
3
O
4
nanoparticles was performed by FE-SEM
technique. The average size of nanoparticle is
32 nm and confirm the spherical and regular
shape of nanoparticles (Fig. 3c). The magnetic
properties of the synthesized nanoparticles were
determined by VSM at room temperature, which
contains the magnetization curve (M) in terms of
the applied magnetic field (H) (hysteresis curve)
of Fe
3
O
4
MNPs particles which shows the great
paramagnetic properties (Fig. 3d).
3.2. The optimization of H
2
O
2
, urea-hydrogen
peroxide and magnetite values
A different combination of magnetite and hydrogen
peroxide was selected for optimization (Table 2).
First, the effect of varying H
2
O
2
and urea-hydrogen
peroxide concentrations on anthracene removal
magnetite was kept constant (Fig. 4). As H
2
O
2
and UHP concentration rises, the removal of
95% at 0.2 mL
H
2
O
2
concentration and 93% at 6 mg UHP content
was observed, respectively. Therefore, the H
2
O
2
and UHP concentrations was optimized for further
experiments. In the next stage, the effect of various
amounts of magnetite on the Fenton oxidation of
anthracene was investigated at optimum H
2
O
2
concentration of 0.2 mL (2.5 mmol) and 6 mg
UHP.
increase in magnetite dosage up to 8 mg, and then
was remained constant at higher concentrations
(Fig. 5). The anthracene removal reached 93% at
the optimum concentration levels of H
2
O
2
, UHP,
and magnetite.
Anthracene removal from soils by Fe3O4-Fenton process Mahdia Hamidinasab et al
Fig. 3. The XRD spectra (a), The FT-IR spectra (b), The FE-SEM image (c)
and The VSM (d) of Fe
3
O
4
nanoparticles
52
Anal. Methods Environ. Chem. J. 4 (3) (2021) 47-58
Table 2. Optimization of combination of magnetite and hydrogen peroxide
Urea-
H
2
O
2
(mg)
Magnetite
(mg)
Samples
H
2
O
2
(ml)
Magnetite (mg)SamplesEntry
310M
10
-UHP
c
3
0.110M
a
10
-H
b
0.1
1
38M
8
-UHP
3
0.18M
8
-H
0.1
2
36M
6
-UHP
3
0.16M
6
-H
0.1
3
610M
10
-UHP
6
0.210M
10
-H
0.2
4
68M
8
-UHP
6
0.28M
8
-H
0.2
5
66M
6
-UHP
6
0.26M
6
-H
0.2
6
1010M
10
-UHP
10
0.310M
10
-H
0.3
7
108M
8
-UHP
10
0.38M
8
-H
0.3
8
106M
6
-UHP
10
0.36M
6
-H
0.3
9
1510M
10
-HUP
15
0.410M
10
-H
0.4
10
158M
8
-UHP
15
0.48M
8
-H
0.4
11
156M
6
-UHP
15
0.46M
6
-H
0.4
12
2010M
10
-UHP
20
---13
208M
8
-UHP
20
---14
206M
6
-UHP
20
---15
a
Magnetite,
b
H
2
O
2
30%
,
c
Urea-H
2
O
2
(UHP)
Fig. 4. (a) H
2
O
2
concentrations
of 0.1-0.4 mL (b) UHP 0.1-0.4 mg (reaction time of 30 min, pH=7 and magnetite concentration of 8 mg)
53
Anthracene removal from soils by Fe3O4-Fenton process Mahdia Hamidinasab et al
Fig. 5.
3
O
4
content in optimized (a) H
2
O
2
and (b) UHP
concentration (reaction time of 30 min and pH=7)
3.3. The effect of contact time on anthracene
removal
The effect of reaction time on anthracene removal at
optimum H
2
O
2
or UHP and magnetite concentration
was investigated (Fig. 6).
The reaction time positively affected the removal
was achieved after 30 min of contact time. After
24 h, about 99% conversion was achieved for all
contaminants.
54
3.4. The blank experiments
After the remediation experiments, two blank
tests were performed. In a sample experiment, 2
ml of deionized water was used without adding
the magnetite and hydrogen peroxide (blank 1) to
contaminated soil. In other sample, only 0.2 mL
H
2
O
2
without magnetite was added (blank 2) to
contaminated soil. The evolution of the conversion
of anthracene in blank 1 and blank 2 is shown in
Figure 7. In the blank 1, the degradation is attributed
to the natural attenuation during the reaction period
(45 days). It is shown the low anthracene content
(20%) in the soil was remediated during 45 days,
which is attributed to biodegradation of anthracene.
Anal. Methods Environ. Chem. J. 4 (3) (2021) 47-58
Fig. 6. The effect of contact time on anthracene removal in optimum H
2
O
2
,
UHP and magnetite concentrations at pH=7
55
The comparative study confirmed the Fenton-
like oxidation capability of the magnetic
nanoparticles for efficient degradation of
anthracene using 8 mg of the nanocatalyst, 0.2
mL H
2
O
2
30 % (2.5 mmol) and 6 mg urea-H
2
O
2
(0.1 mmol) at neutral pH as optimum operational
parameters under mild reaction conditions.
The solid urea-H
2
O
2
is
safer
than liquid H
2
O
2
(Fig. 8a). The magnetite (Fe
3
O
4
) is an efficient
nanocatalyst for the degradation of anthracene
and the urea-H
2
O
2
with lower content has a better
oxidizing effect than H
2
O
2
(Fig. 8b).
Anthracene removal from soils by Fe3O4-Fenton process Mahdia Hamidinasab et al
Fig. 7. The blank experiments in optimum oxidation condition
Fig. 8. (a) The sign of acute exposure of skin to hydrogen peroxide (H
2
O
2
30%)
(b) The comparison of H
2
O
2
and urea-H
2
O
2
as oxidants in Fenton’s method
56
4. Conclusions
In the present study, the Fenton-like oxidation
capability of the magnetite nanoparticles for the
urea-H
2
O
2
with lower content has a better oxidizing
effect than H
2
O
2
. Furthermore, the solid urea-H
2
O
2
is
safer
than liquid H
2
O
2
. The natural concentration
attenuation during the treatment time (45 days) was
less than 20% of the anthracene in soil. It was stated
that the magnetite nanocatalyst could activate
molecular oxygen via single-electron reduction
pathway to produce reactive oxygen species,
including hydroxyl radical (OH), which are
capable of oxidizing contaminants. The generated
hydroxyl radicals oxidized the polycyclic aromatic
hydrocarbon contaminants by breaking them down
into non-toxic products. Therefore, the magnetite/
UHP system is a promising and environmentally
benign catalytic process for the remediation of
PAH-contaminated soils.
5. Acknowledgements
The Authors gratefully acknowledge the research
council of Arak University and department of
chemistry for providing the chemicals and apparatus.
6. Declaration of funding
The Authors gratefully acknowledge the partial
support from the research council of Arak
University.
7. References
[1] L. Wu, R. Sun, Y. Li, C. Sun, Sample preparation
and analytical methods for polycyclic aromatic
hydrocarbons in sediment, Trends Environ.
Anal. Chem., 24 (2019) e00074.
[2] Y. Sun, S. Wu, G. Gong, Trends of research
on polycyclic aromatic hydrocarbons in food:
A 20-year perspective from 1997 to 2017,
Trends food sci. technol., 83 (2019) 86-98.
[3] H.K. Bojes, P.G. Pope, Characterization
of EPA’s 16 priority pollutant polycyclic
aromatic hydrocarbons (PAHs) in tank
bottom solids and associated contaminated
soils at oil exploration and production sites in
Texas, Regul. Toxicol. Pharmacol., 47 (2007)
288–295.
[4] X.P. Yang, L.X. Xie, J. Tang, J. Lin, Removal
and degradation of phenanthrene and pyrene
from soil by coupling surfactant washing
with photocatalysis, Appl. Mech. Mater., 446
(2014) 1485–1489.
[5] S. Kuppusamy, P. Thavamani, K.
Venkateswarlu, Y.B. Lee, R. Naidu,
M. Megharaj, Remediation approaches
for polycyclic aromatic hydrocarbons
(PAHs) contaminated soils: Technological
constraints, Emerg. Trends Future Directions,
168 (2017) 944-968.
[6] M. Usman, P. Faure, K. Hanna, M. Abdelmoula,
C. Ruby, Application of magnetite
catalyzed chemical oxidation (Fenton-like
and persulfate) for the remediation of oil
hydrocarbon contamination,Fuel., 96 (2012)
270–276.
[7] R. Andreozzi, V. Caprio, A. Insola, R.
Marotta, Advanced oxidation processes
Catal. Today, 53 (1999) 51–59.
[8] Q. Zhou, Y. Wang, J. Xiao, H. Fan, C. Chen,
Preparation and characterization of magnetic
nanomaterial and its application for removal
of polycyclic aromatic hydrocarbons, J.
Hazard. Mater., 371 (2019) 323–331.
[9] A. Romero, A. Santos, F. Vicente, S.
Rodriguez, A.L. Lafuente, In situ oxidation
remediation technologies: Kinetic of
hydrogen peroxide decomposition on soil
organic matter, J. Hazard. Mater., 170 (2009)
627–632.
[10] J. Shao, F. Lin, Z. Wang, P. Liu, H. Tang,
Y. He, K. Cen, Low temperature catalytic
based catalysts: Effect of support property
and SO
2
/water vapor addition, Appl. Catal.
B: Environ., 266 (2020) 118662.
[11] C.M. Kao, K.D. Huang, J.Y. Wang, T.Y.
Chen, H.Y. Chien, Application of potassium
Anal. Methods Environ. Chem. J. 4 (3) (2021) 47-58
57
permanganate as an oxidant for in situ
oxidation of trichloroethylene-contaminated
groundwater: A laboratory and kinetics study,
J. Hazard. Mater., 153 (2008) 919–927.
[12] J.A. Khan, X. He, H.M. Khan, N.S. Shah,
D.D. Dionysiou, Oxidative degradation of
atrazine in aqueous solution by UV/H
2
O
2
/
Fe
2+
, UV/S
2
O
8
2-
/Fe
2+
and UV/HSO
5-
/Fe
2+
processes: A comparative study, Chem. Eng.
J., 218 (2013) 376–383.
[13] K. Ayoub, E.D. van Hullebusch, M. Cassir, A.
Bermond, Application of advanced oxidation
processes for TNT removal: A review, J.
Hazard. Mater., 178 (2010) 10-28.
[14] M. Bellardita, V. Loddo, A. Mele, W.
Panzeri, F. Parrino, I. Pibiri, L. Palmisano,
Photocatalysis in dimethyl carbonate green
solvent: Degradation and partial oxidation of
phenanthrene on supported TiO
2
, RSC Adv.,
4 (2014) 40859–40864.
[15] M. Ruokolainen, T. Gul, H. Permentier,
T. Sikanen, R. Kostiainen, T. Kotiaho,
Comparison of TiO
2
photocatalysis,
electrochemically assisted Fenton reaction
and direct electrochemistry for simulation of
phase metabolism reactions of drugs, Eur. J.
Pharm. Sci., 83 (2016) 36–44.
[16] S.N. Malik, P.C. Ghosh, A.N. Vaidya, S.N.
Mudliar, Hybrid ozonation process for
industrial wastewater treatment: Principles
and applications: A review, J. Water Process
Eng., 35 (2020) 101193.
[17] K. Ayoub, E.D. Van Hullebusch, M. Cassir, A.
Bermond, Application of advanced oxidation
processes for TNT removal: A review, J.
Hazard. Mater., 178 (2010) 10–28.
[18] M.D. Nicodemos Ramos, L.A. Sousa, A.
Aguiar, Effect of cysteine using Fenton
processes on decolorizing different dyes: a
kinetic study, Environ. Technol., 57 (2020)
1–132.
[19] C.M. Dominguez, A. Romero, A. Santos,
Selective removal of chlorinated organic
compounds from lindane wastes by
combination of nonionic surfactant soil
J., 376 (2019) 120009.
[20] C.G.S. Lima, N.M. Moreira, M.W. Paixão,
A.G. Corrêa, Heterogenous green catalysis:
Application of zeolites on multicomponent
reactions, Curr. Opin. Green Sustain.
Chem., 15 (2019) 1-7.
[21] P.T. Silva, V.L. da Silva, B. de B. Neto, M.O.
Simonnot, Phenanthrene and pyrene oxidation
in contaminated soils using Fenton’s reagent,
J. Hazard. Mater., 161 (2009) 967–973.
[22] F. Pardo, M. Peluffo, A. Santos, A. Romero,
Optimization of the application of the
Fenton chemistry for the remediation of a
contaminated soil with polycyclic aromatic
hydrocarbons, J. Chem. Technol. Biotechnol.,
91 (2016) 1763–1772.
[23] G. Vilardi, D. Sebastiani, S. Miliziano, N.
Verdone, L. Di Palma, Heterogeneous nZVI-
induced Fenton oxidation process to enhance
biodegradability of excavation by-products,
Chem. Eng. J., 335 (2018) 309–320.
Mora, Clays and oxide minerals as catalysts
and nanocatalysts in Fenton-like reactions - A
review, Appl. Clay Sci., 47 (2010) 182–192.
[25] Y. Wang, Y. Gao, L. Chen, H. Zhang, Goethite
for the degradation of methyl orange, Catal.
Today, 252 (2015) 107–112.
[26] M. Lu, Z. Zhang, W. Qiao, Y. Guan, M. Xiao,
C. Peng, Removal of residual contaminants
in petroleum-contaminated soil by Fenton-
like oxidation, J. Hazard. Mater., 179 (2010)
604–611.
[27] M. Munoz, Z.M. de Pedro, J.A. Casas,
J.J. Rodriguez, Preparation of magnetite-
based catalysts and their application in
heterogeneous Fenton oxidation - A review,
Appl. Catal. B: Environ., 176 (2015) 249-
265.
[28] S. Rostamnia, B. Gholipour, X. Liu, Y.
Wang, H. Arandiyan, NH
2
-coordinately
immobilized tris(8-quinolinolato)iron onto
the silica coated magnetite nanoparticle:
Anthracene removal from soils by Fe3O4-Fenton process Mahdia Hamidinasab et al
58
Fe
3
O
4
@SiO
2
-FeQ
3
as a selective Fenton-like
Colloid Interface Sci., 511 (2018) 447–455.
[29] H.Y. Xu, B. Li, T.N. Shi, Y. Wang, S.
Komarneni, Nanoparticles of magnetite
anchored onto few-layer graphene: A highly
J. Colloid Interface Sci., 532 (2018) 161–170.
[30] C.H. Han, H.D. Park, S.B. Kim, V. Yargeau,
J.W. Choi, S.H. Lee, J.A. Park, Oxidation
of tetracycline and oxytetracycline for the
photo-Fenton process: Their transformation
products and toxicity assessment, Water Res.,
172 (2020) 115514.
[31] S.S. Li, Z. Tian, D.Z. Tian, L. Fang, Y.W. Huang,
of Magnetic Fe
3
O
4
Nanoparticles, Adv. Sci.
Eng. Med., 12 (2020) 131–136.
[32] W. Mäntele, E. Deniz, UV–VIS absorption
spectroscopy: Lambert-Beer reloaded,
Spectrochim. Acta Part A: Mol. Biomol.
Spec., 173 (2017) 965–968.
[33] V.C. Mora, L. Madueño, M. Peluffo, J.A.
Rosso, M.T. Del Panno, L.S. Morelli,
Remediation of phenanthrene-contaminated
soil by simultaneous persulfate chemical
oxidation and biodegradation processes,
Environ. Sci. Pollut. Res., 21 (2014) 7548–
7556.
[34] Z. Najahi Mohammadizadeh, M. Hamidinasab,
N. Ahadi, M.A. Bodaghifard, A novel hybrid
organic-inorganic nanomaterial: preparation,
characterization and application in synthesis
of diverse heterocycles, Polycycl. Aromat.
Compd., (2020). https://doi.org/10.1080/1040
6638.2020.1776346
Anal. Methods Environ. Chem. J. 4 (3) (2021) 47-58
Anal. Methods Environ. Chem. J. 4 (3) (2021) 59-67
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
A fast, low-cost and eco-friendly method for routine
vortex assisted liquid-liquid extraction
Gustavo Waltzer Fehrenbach
a
, Daniel Ricardo Arsand
a,*
, Sergiane Caldas Barbosa
b
, Katia R L Castagno
a
,
Pedro Jose Sanches Filho
a
and Ednei Gilberto Primel
b
a
Chemistry Department. Sul-rio-grandense Federal Institute of Education, Science and Technology,
360-96015, Praça 20 de Setembro – 455, Pelotas, RS, Brazil.
b
School of Chemistry and Food. Federal University of Rio Grande, 900-96203, Av. Itália - Km 8, Rio Grande, RS, Brazil.
ABSTRACT
variety of urban solid wastes (USW). The decomposition and
biodegradation processes generate a leachate of high complexity and
toxicity, containing persistent and recalcitrant contaminants that are
not usually monitored. Bisphenol-A (BPA) is a synthetic compound
applied mostly on the production of polycarbonate plastics, epoxy
resins, and is an endocrine disruptor. BPA negatively affects biological
receptors, resulting in harmful effects to nervous and reproductive
system as well metabolic and immune function. The presence of BPA in
USW urges the development of feasible analytical methods to support
fast and simple method for routine analysis of BPA in the leachate
using 1-octanol as solvent was performed. BPA recoveries at spiking
levels of 2.5, 6.5 and 12.5 µg L
-1
were between 60 to 104% with
relative standard deviation (RSD) lower than 26%. The linearity
-1
with a pre-
concentration factor of 20. The method has advantages such as low
consumption of extraction solvent (150 µL), low cost, easy and fast
determination.
Keywords:
Endocrine disruptors,
VALLME,
Bisphenol-A,
Contaminant
ARTICLE INFO:
Received 5 Jun 2021
Revised form 9 Aug 2021
Accepted 30 Aug 2021
Available online 29 Sep 2021
*Corresponding Author: Daniel Ricardo Arsand
Email: danielarsand@pelotas.ifsul.edu.br
https://doi.org/10.24200/amecj.v4.i03.146
------------------------
1. Introduction
Bisphenol-A (BPA) is a synthetic compound
of wide applicability used in the synthesis of
materials as detergents, polycarbonates, thermal
paper, epoxy resin, and food packaging [1]. It
a structure similar to the steroid hormone
the estrogen activity [1-3]. BPA effects were
discussed in neurochemistry alterations, prostate
cancer, breast cancer, hormonal alterations,
infertility, and ovaries problems [1, 4, 5]. The
usage of BPA in packs of plastic, thermal papers,
coating of food cans, pharmaceuticals, and
general industry represents a direct source for
human and environment contamination [6,7]. In
60
sites. These sites are projected to work in a long
and slowly process of degradation. Although,
degradation processes as photolysis, hydrolysis
and biological still occurs and generates a leachate
of high complexity and toxicity, where the
presence of BPA threatens the environment safety
[8, 9]
to evaluate the trace levels of BPA in the complex
matrix of leachate. For that, a pre-concentration
and/or clean-up step have been used to prepare
the sample prior to extraction and analytical
of BPA at trace levels in water and plastic
materials as toys. [10, 11]. In general, the sample
preparation has been performed by methods based
on liquid or solid phase extraction. In the solid
phase extraction (SPE), the analyte is extracted
from the sample by passing the sample through a
column/cartridge packed with polar (e.g. alumina)
solid phase microextraction (SPME) have also
been observed for BPA extraction. On the other
hand, liquid-liquid extraction (LLE) methods
are based on the usage of solvents to extract and
separate the analyte from the matrix, usually in
an aqueous and organic phase [7, 11, 13, 14].
SPE and LLE have been used and adapted for
years and their application is well dependent to
the matrix composition, sample properties and
concentration. However, there is a need for non-
tedious and environmentally friendly methods,
employing lower volumes of non-toxic solvents
liquid microextraction (VALLME) is a technique
extraction applies reduced volumes of a low-
density solvent into water associated with high
energy of vortex mixing [15]
can rapidly extract target analytes from water due
to shorter diffusion distance and larger interfacial
phase restores its initial single-drop shape for the
following instrumental analysis. This technique
has showed to be eco-friendly for BPA extraction
in water samples [16]. Gas chromatography (GC)
and high-pressure liquid chromatography (HPLC)
are the main analytical instruments used for BPA
detection. Either are based on the difference of
interaction between the sample in mobile phase
(liquid for HPLC, and gas for GC) and stationary
phase (packed column). Then, the analyte interacts
with the detector that generates an electronic
signal, translated into a peak. Different GC and
HPLC setups have already been described.
The mass spectrometry (MS), ultraviolet (UV)
in HPLC, while in GC the MS have been more
applied for the detection of BPA [3, 5, 10-15]. In
this work, the usage of HPLC with diode-array
detector has been chosen due advantages as the
simultaneous acquisition in different wavelengths,
improving the separation of peaks, an important
factor to be considered when working with
complex matrices as leachate [11, 14, 15]. The
challenges of controlling the destiny of USW to
discard is aggravated by the analytical limitations
complex matrices. On this way, a feasible and low-
cost method could collaborate with better health
policies and increase the alert to BPA exposure.
The aim of this study was to develop a fast, robust,
low-cost and accuracy method for routine analysis
employing VALLME and HPLC-DAD.
2. Material and Methods
2.1. Chemical and samples
The bisphenol A (BPA) standard and analytical
grade acetonitrile (J.T Baker, Mallinckrodt, NJ,
USA) were purchased from Sigma-Aldrich (São
Paulo, Brazil). BPA standard solutions were
prepared in methanol and stored at 4 ºC until use.
Ultrapure water was prepared in a Direct-Q UV3
(Millipore, France), and used as mobile phase as
well as acetonitrile.
The leachate used in this study was collected
according to standard methods (SM:2005) from a
Anal. Methods Environ. Chem. J. 4 (3) (2021) 59-67
61
The samples were stabilized with H
2
SO
4
(1 mol
L
-1
) and kept in the dark at 4 ºC until the analytical
out with a Micropore system using cellulose acetate
membranes of 0.45 µm (Sartorius Biolab Products,
Goettingen, Germany), assisted with vacuum from a
vacuum-pump Tecnal TE-0581 (Tecnal, São Paulo,
Brazil), and kept in a pre-washed amber bottle with
acetone aqueous solution 1 mol L
-1
.
2.2. Apparatus
The BPA determination was carried out in a Waters
high performance liquid chromatography coupled
to a diode array detector 2996 (Waters, Milford,
MA, USA), equipped with a quaternary pump
model 600, Empower PDA software was employed
on the data acquisition. The separation was realised
in a silica-based, reversed-phased analytical
column C18 5 µm ODS2 150 mm x 4.6 (Waters,
Milford, MA, USA). The analytes were eluted with
a mixture of ultrapure 60% H
2
O and 40% analytical
grade ACN as mobile phase in isocratic mode and
-1
. The injection was made
manually using a syringe with 20 µL of VALLME
extracted sample.
2.3. Vortex-assisted liquid-liquid microextraction
procedure
VALLME extractions were carried out in 10 mL
glass tubes with conical bottom with 10 mL
quadruplicate (Sigma-Aldrich, São Paulo, Brazil).
The tubes were vortexed (Certomat MV, B. Braun
Biotech International) at 4500 rpm for 5 min,
and centrifuged at 2000 rpm for 5 min (Quimis,
São Paulo, Brazil). The supernatant was taken
out after phase separation with a 250 µL syringe
and transferred to 2 mL tube (Eppendorf 5804
R, Eppendorf, São Paulo, Brazil). The 2 mL tube
was centrifuged once more at 2000 rpm for 2 min
and the supernatant was collected with a syringe,
transferred to a new
to 0.5 mL with methanol. The parameters related
to VALLME and HPLC-DAD were adjusted
before the validation process. The lowest volume
of solvent and sample that resulted in a detectable
and reliable signal of BPA were chosen. Vortex and
centrifugation were based on the visual formation
and stability of the organic layer. Then, a second
centrifugation was realised to remove possible
contaminants carried by the pipetting. Five hundred
microliters of methanol were used to ensure the
complete resuspension of organic phase (Fig.1).
Determination of Bisphenol-A by VALLME Gustavo Waltzer Fehrenbach et al
Fig. 1. Vortex-assisted liquid-liquid microextraction (VALLME) procedure.
62
2.4. Analytical performance
The proposed method was validated by analysing
parameters as analytical curve, linearity, limit of
recovery and precision (intermediate precision and
repeatability), according to Brazilian legislation
(INMETRO - DOQ-CGCRE - 008, 2011) which
stablish the procedures and standards for analytical
determinations. Accuracy was evaluated using
recovery experiments with extraction of 3 different
BPA standard concentrations: 2.5, 6.25 and 12.5
µg L
-1
. The precision in terms of repeatability was
obtained by carrying out the extraction and analysis
in three replicates and each extract injected three
times in the HLPC-DAD equipment. Different days
were used for the same spike levels of repeatability
to evaluate the intermediate precision of the
method. Limit of detection (LOD) and the limit of
signal/noise 3:1 and 10:1, respectively.
3. Results and discussion
3.1. Preliminary analysis
from different sources. The wide application of
BPA and indiscriminate holding of plastic materials
at these sites represents a direct source for BPA
to contaminate soil, water, and environment,
posteriorly reaching human by direct contact or
indirect through contaminated food. Due to the
matrix complexity and low concentrations, a
method to identify and quantify estrogens need to
[17]. A standard solution
of BPA was diluted in methanol (mobile phase) and
added to leachate sample to verify the presence of
interferences in the absorption spectrum of BPA,
required to avoid false positive results. The retention
time for BPA standard in methanol was at 5.8 min
of run and detection wavelength at 227 nm. BPA
retention time as in methanol. The chromatogram
in Figure 2, and it can be observed the absence of
interference at BPA retention time (5.8 min) and
Anal. Methods Environ. Chem. J. 4 (3) (2021) 59-67
Fig. 2.
No interference was detected at retention time for BPA (5.8 min)
63
3.2. Validation of analytical procedure
The determination of analyte concentration in
different matrices is usually made by a calibration
curve, preparing concentrations of stock
standard solution and relating to absorbance
units obtained for each concentration, generating
an equation used to quantify the analyte in real
samples. Furthermore, this procedure is also
applied to measure the correlation between
2 factors, a necessary factor in the process of
validation. The maximum value for correlation
coefficient (r) is 1, ensuring the relation between
absorbance and concentration. The calibration
curve was prepared with 5 concentrations of
standard BPA in methanol, ranging from 0.05
to 2.5 mg L
-1
(n= 3). The curve showed a high
linear correlation (r) of 0.9985, overcoming
the requirements stablished by the Brazilian
legislation (ANVISA: 0.99 and INMETRO:
0.90) and allowing the use to determine BPA in
leachate sample.
LOD and LOQ represents the limits of detection
as the smaller concentration of analyte that can
be detected without guarantee or reliability. LOQ
is the lowest concentration where the analyte can
be determined with precision. Appling the ratio
signal-noise to obtain the LOD (3:1) and LOQ
(10:1), the values found were 0.8 and 2.5 µg L
-1
,
respectively. These values are in agreement with
other microextraction techniques proposed for
BPA detection as showed in Table 1. Recoveries
were determined in 2.5, 6.25 and 12.5 µg L
-1
levels
(Fig. 3), obtaining an RSD from 60 to 104% and
RSD from 11 to 26%. Intermediate precision was
determined in different days of analyses and the
recoveries obtained were between 81% and 97%
with RSD lower than 16%.
Determination of Bisphenol-A by VALLME Gustavo Waltzer Fehrenbach et al
Fig. 3. Evaluation of method accuracy, repeatability, and intermediate precision
-1
)
64
The highest recoveries and consequently accuracy,
repeatability and intermediate precision were
obtained with 12.5 µg L
-1
of BPA. These results can
also be observed in Table 1, where are presented
the corresponding recoveries of 2.5, 6.25, and 12.5
µg L
-1
the chromatograms (Fig. 4) of BPA in methanol
(4a) (4b).
In the Table 2 are presented the results of BPA
determination in diverse matrices less complex than
in our research agree with the literature for BPA
extraction from liquid samples: SPE [7] with serial
processes of homogenization-vortex-sonication-
centrifugation-evaporation-resuspension of
sample [18], Micro-QuEChERS-GC/MS [19],
and DLLME [20]. Correia-Sá et al [19] obtained
recoveries of BPA from 70 to 120% and RSD
from 3 to 11% applying Micro-QuEChERS-GC/
leachate. Laganà et al [17] obtained 99-103%
Anal. Methods Environ. Chem. J. 4 (3) (2021) 59-67
Table 1.
-1
of BPA stock.
Results are based on the recoveries obtained for the respective stock in methanol.
Stock (µg L
-1
)
Samples (%recovery)
1 2 3 4 5
2.5 69.89 73.87 38.87 75.93 40.28
6.25 103.46 110.89 105.49 95.13 95.73
12.5 97.00 93.24 114.55 117.02 80.66
Fig. 4. Chromatogram of BPA standard solution (a)(b).
The signals were generated with 12.5 µg L
-1
of BPA
65
As showed in Figure 4, BPA can be determined
interference and reliable results, followed by
easily detection. The method is also eco-friendly,
requiring less than 1 mL of solvent per analysis
and not time demanding.
The protocol in this method is ideal for routine
and quick analysis, versatile and can be used in
a broad spectrum of matrix with high extraction
rates, easy cleanup step, low RSD, feasibility, low
consumption of solvents, and non-expensive.
4. Conclusions
On this article we developed an analytical
leachate. A low volume of 1-octanol (150 µL) was
used as extraction solvent in the vortex-assisted
liquid-liquid microextraction (VALLME) in a
simple procedure that takes around 20 min to be
executed. The proposed method was validated
by adding standard concentrations of BPA in
leachate and quantifying the recoveries, with
a full analysis of standard deviation, accuracy,
repeatability, intermediate precision, LOD, and
LOQ. BPA recoveries were between 60 to 104%
with relative standard deviation (RSD) lower
than 26%, and linearity of 0.9985. The limit of
-1
with a pre-
concentration factor of 20. Thereby, the proposed
methodology is eco-friendly, requiring a low
volume of sample and extraction solvent. The
method present technical features that adequate
for BPA routine analysis and also the potential
matrices.
5. Declaration of interest
6. Acknowledgements
The authors are grateful to the Brazilian National
Development (CNPq) for providing grants for this
study, to Sul-rio-grandense Federal Institute for
Education, Science and Technology (IFSul) and to
support.
7. References
[1] Y. Ma, H. Liu, J. Wu, L. Yuan, Y. Wang, X.
Du, R. Wang, P.W. Marwa, P. Petlulu, X.
Chen, H. Zhang, The adverse health effects of
bisphenol A and related toxicity mechanisms,
Environ. Res., 176 (2019) 108575.
[2] R. B. Gear, S. M. Belcher, Impacts of
Bisphenol A and ethinyl estradiol on male
and female CD-1 mouse spleen, Sci. Rep., 7
(2017) 856.
Determination of Bisphenol-A by VALLME Gustavo Waltzer Fehrenbach et al
Table 2.
(RSD%) of BPA determination methods obtained by different authors in diverse matrices and complexities.
Matrix Recoveries (%) LOQ LOD RSD (%) References
60-104 2.5 µg L
-1
0.8 µg L
-1
11-26 **
Urine 0-120 0.43 µg L
-1
0.13 µg L
-1
3-11 [19]
88.6-96.2
-1
ng L
-1
* 1.5-15 [21]
Blood serum 101-106 0.028 ng mL
-1
0.009 ng mL
-1
3.9-5.8 [22]
River water 84.7-95.7 0.01 ng mL
-1
0.003 ng mL
-1
5.3-9.6 [23]
bottled and surface water
89-113 6; 24 and 7 ng L
-1
20; 7; 22 ng L
-1
<17 [24]
estuarine water
89-94 11-20 ng L
-1
*
2-13 [25]
66
Anal. Methods Environ. Chem. J. 4 (3) (2021) 59-67
[3] S. M. Zimmers, E. P. Browne, P. W.
O’Keefe, D. L. Anderton, L. Kramer, D. A
Reckhow, K. F. Arcaro, Determination of
free Bisphenol A (BPA) concentrations in
breast milk of U.S. women using a sensitive
LC/MS/MS method, Chemospher, 104
(2014) 237-243.
[4] Y-K. Leung, V. Govindarajah, A. Cheong, J.
Veevers, D. Song, R. Gear, X. Zhu, J. Ying, A.
Kendler, M. Medvedovic, S. Belcher, S-M.
Ho, Gestational high-fat diet & bisphenol A
exposure heightens mammary cancer risk,
Endocr. Relat. Cancer, 24 (2017) 365-378.
treatment for the determination of bisphenol
A and its chlorinated derivatives in sewage
sludge samples by pressurized liquid
extraction and liquid chromatography-
tandem mass spectrometry, Talanta, 101
(2012) 01-10.
[6] S. Almeida, A. Raposo, M. Almeida-
González, C. Carrascosa, Bisphenol A: Food
Exposure and Impact on Human Health,
Compr. Rev. Food Sci. Food Saf., 17 (2018)
1503-1517.
[7] X. Hu, X. Wu, F. Yang, Q. Wang, C. He,
S. Liu, Novel surface dummy molecularly
imprinted silica as sorbent for solid-phase
extraction of bisphenol A from water
samples, Talanta, 148 (2016) 29-36.
from South East Europe, Environ. Sci.
Pollut. Res., 28 (2021) 42196–42203.
[9] H. Wang, H. Yan, C. Wang, F. Chen, M.
Ma, W. Wang, X. J. Wang, Analysis of
phenolic pollutants in human samples by
high performance capillary electrophoresis
based on pretreatment of ultrasound-
Chromatogr. A, 1253 (2012) 16-21.
[10] Y. Vicente-Martinez, M. Caravaca, A.
Soto-Meca, Determination of very low
concentration of bisphenol A in toys and
microextraction by In situ ionic liquid
formation and high-performance liquid
chromatography, Pharmaceuticals, 13 (2020)
301.
[11] P-P, Hao, Determination of bisphenol A
in barreled drinking water by a SPE–LC–
MS method, J. Environ. Sci. Health A Tox.
Hazard. Subst. Environ. Eng., 55 (2020) 697-
703.
[12] M. Caban, O. Stepnowaski, The
analogues in wastewaters and surface water
by an improved solid-phase extraction gas
chromatography/mass spectrometry method,
Environ. Sci. Pollut. Res., 27 (2020) 28829-
28839.
[13] S. Cho, Y. S. Choi, H. M. D. Luu, J. Guo,
Determination of total leachable bisphenol
A from polysulfone membranes based on
multiple consecutive extractions, Talanta,
101 (2012) 537-540.
[14] M. Sadeghi, Z. Nematifar, N. Fattahi, M.
Pirsaheb, M. Shamsipur, Determination
of bisphenol A in food and environmental
samples using combined solid-phase
extraction-dispersive liquid-liquid
organic drop followed by HPLC, Food Anal.
Methods, 9 (2016) 1814-1824.
[15] R. Amini, J. Khandaghi, M. R. A. Mogaddam,
Combination of vortex-assisted liquid–
liquid extraction and air-assisted liquid–
liquid microextraction for the extraction of
bisphenol A and bisphenol B in canned doogh
samples, Food Anal. Methods, 11 (2018)
3267-3275.
[16] C. Bosch Ojeda, F. Sánchez Rojas, Vortex-
assisted liquid–liquid microextraction
(VALLME): applications, Chromatographia,
77 (2014) 745-754.
[17] A. Laganà, A. Bacaloni, I. De Leva, A. Faberi,
67
Determination of Bisphenol-A by VALLME Gustavo Waltzer Fehrenbach et al
G. Fago, A. Marino, Analytical methodologies
for determining the occurrence of endocrine
disrupting chemicals in sewage treatment
plants and natural waters, Anal. Chim. Acta,
501 (2004) 79-88.
[18] A. Cariot, A. Dupuis, M. Albouy-Llaty, B.
Legube, S. Rabouan, V. Migeot, Reliable
chlorinated derivatives in human breast milk
using UPLC-MS/MS method, Talanta, 100
(2012) 175-182.
[19] L. Correia-Sá, S. Norberto, C. Delerue-
Matos, C. Calhau, V. F. J. Domingues, Micro-
QuEChERS extraction coupled to GC-MS for
a fast determination of Bisphenol A in human
urine, Chromatogr. B, 1072 (2017) 9-16.
Afonso, ‘In-situ ionic liquid-dispersive liquid-
liquid microextraction method to determine
endocrine disrupting phenols in seawaters
174 (2011) 213-222.
[21] X. Sun, J. Peng, M. Wang, C. Tang, L.Yang, H.
Lei, F. Li, X. Wang, J. J. Chen, Determination
of nine bisphenols in sewage and sludge
using dummy molecularly imprinted
solid-phase extraction coupled with liquid
chromatography tandem mass spectrometry,
Chromatogr. A, 1552 (2018) 10-16.
[22] K. Owczarek, P. Kubica, B. Kudlak, A.
levels of bisphenol A analogues in human
blood sérum by high performance liquid
chromatography-tandem mass spectrometry,
Sci. Total Environ., 628-629 (2018) 1362-
1368.
[23] Z. Wang, J. Yu, L.Wu, H. Xiao, J. Wang,
analogues in environmental samples using
precolumn derivatization and ultra high
performance liquid chromatography with
tandem mass spectrometry, Separation Sci.,
41 (2018) 2269-2278.
V. Sancho, M. Ibáñez, A. F. Roig-Navarro,
Method development and validation for the
determination of selected endocrine disrupting
compounds by liquid chromatography
mass spectrometry and isotope pattern
deconvolution in water samples: comparison
of two extraction techniques, Anal. Methods,
8 (2016) 2895-2903.
[25] O. Ros, A. Vallejo, L. Blanco-Zubiaguirre,
M. Olivares, A. Delgado, N. Etxebarria, A.
Prieto, Microextraction with polyethersulfone
for bisphenol-A alkyphenols and hormones
determination in water samples by means of
gas chromatography-mass spectrophotometry
and liquid chromatography-tandem mass
spectrometry analysis, Talanta, 134 (2015)
247-255.
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Thallium extraction in urine and water samples by
nanomagnetic 4-Aminothieno[2,3-d] pyrimidine-2-thiol
functionalized on graphene oxide
Seyed Jamilaldin Fatemi
a,*
, Mohammad Reza Akhgar
b
and Masoud Khaleghi Abbasabadi
c
a
Department of Chemistry, Shahid Bahonar University of Kerman, 133 -76169, Kerman, Iran
b
Department of Chemistry, Faculty of Science, Kerman Branch, Islamic Azad University, Kerman, Iran
C
Researcher in Nano Technology Center, Research Institute of Petroleum Industry (RIPI), P.O. Box 1998-14665, Tehran, Iran
ABSTRACT
Thallium is a water-soluble metal and extra dosage has toxicological
effect in human body. Thallium is readily absorbed by inhalation,
ingestion and skin contact. The symptomatology of thallium toxicity
was seen in patients with hemorrhage, bone/gastrointestinal problems,
delirium, convulsions and coma. So, accurate determination of
thallium in water and human urine is necessary. In this research,
a novel and applied method based on 25 mg of nanomagnetic
4-Aminothieno[2,3-d] pyrimidine-2-thiol functionalized on graphene
oxide (Fe
3
O
4
-ATPyHS@GO) was used for thallium extraction in 50
mL of water, wastewater and urine samples by dispersive magnetic
back-extraction of solid phase by 1 mL of nitric acid solution, the
spectrometry (F-AAS). The working/linear range, the limit of detection
(LOD), and preconcentration factor (PF) were achieved (4-1400
L
; 4-300 L
), 0.9 µg L
, and 50, respectively (Mean RSD%=1.8
water; 2.1 urine). The absorption capacity of GO and Fe
3
O
4
-ATPyHS@
GO adsorbent were achieved 7.2 mg g
-1
and 137.5 mg g
-1
for 5 mg
L
-1
of thallium, respectively. The procedure was validated by ICP-MS
analyzer.
Keywords:
Thallium,
Water and urine,
Nanomagnetic 4-Aminothieno[2,3-d]
pyrimidine-2-thiol functionalized on
graphene oxide,
Dispersive magnetic micro solid-phase
extraction
ARTICLE INFO:
Received 20 May 2021
Revised form 18 Jul 2021
Accepted 13 Aug 2021
Available online 28 Sep 2021
*Corresponding Author: Seyed Jamilaldin Fatemi
Email: fatemijam@uk.ac.ir
https://doi.org/10.24200/amecj.v4.i03.150
------------------------
1. Introduction
The Thallium use as in semiconductor and
optical industries. The concentration of
thallium in rocks and soil (limestone, granite)
ranges between 0.05-1.7 mg kg
and 1.7-55
mg kg
, respectively [1]. The organic slates
and carbon source have 1000 mg kg
thallium
[2], and high concentration of thallium exist
sulfur salts of thallium [3]. Contamination with
thallium is effected on the environmental and
human health. Thallium has toxic effect even at
sub ppb concentration and accumulate in plant,
vegetables, fruit, microorganisms, animals and
human tissues due to water soluble [4,5]. The
occupational exposure of thallium is 0.1 mg m
-2
for skin and more than 15 mg m
-2
is dangerous for
human. Thallium can be absorbed from inhalation,
ingestion and skin. So, the thallium toxicity must
be evaluated in patients through determination
in water, wastewater, urine, hair, nail and blood
samples. The toxicity of this element is higher
compared to mercury, cadmium and lead [6,7].
The mean daily diet contains 2 ng L
-1
thallium
69
Thallium extraction by Fe
3
O
4
et al
and the average content of thallium in the human
body was 0.1 mg. The concentrations in blood
and due to reference values
thallium has low concentration between 0.15–0.6
in serum
[8,9]. Groesslova and Wojtkowiak showed that
the toxicity of thallium is mainly related to the
similarity between Tl (I) ions and K ions, which
cause to the thallium interference with potassium
and disorder of potassiumassociated metabolic
processes. Also,
bonds and cysteine cross-linking and cause to
the keratin reduction [10,11]. The thallium-201,
a radioactive isotope, was used for evaluating
coronary artery disease. This type of thallium is
more than 4000 times less potent. Thallium-201
is useful in distinguishing toxoplasmosis from
Primary CNS lymphoma (PCNSL)in HIV
patients. Also, the thallium-201 scintigraphy
is useful to diagnose the Kaposi sarcoma, the
thyroid imaging and various tumors of the
lungs [12]. the acute thallium toxicity has been
reported between 6-15% in humans by health
organization and the dosage from 10 to 15 mg
kg
-1
is a lethal dose for humans. Elimination phase
for thallium stats about 24 hours’ post-exposure
and is mainly achieved through renal excretion
and the elimination phase may take up to 30 days
with long time. Symptoms of acute exposure
of thallium are gastrointestinal, CNC problem,
and skin [13,14]. The chronic exposure is
gastrointestinal symptoms include, the abdominal
pain, the vomiting and the diarrhea. Therefore,
due to adverse effect of thallium in human health,
the determination human urine, foods and waters
must be considered [15]. Based on the thallium
toxicity, the power technique must be used
for determining of thallium in environmental
(water) and human biological (urine) samples.
Numerous papers showed that the measurement
of this topic with different analytical methods
in various matrixes such as, the laser excited
[16], the anodic stripping voltammetry (ASV)
[17], the inductively coupled plasma optical
emission spectrometry (ICP-OES) [18]
atomic absorption spectrometry (FAAS) [19], the
electrothermal atomic absorption spectrometry
(ET- AAS) [19] and the high resolution inductively
coupled plasma mass spectrometry (HR-ICP-MS)
[20].
In this research, a novel method based on
nanomagnetic 4-Aminothieno[2,3-d] pyrimidine-
2-thiol functionalized on graphene oxide as a
Fe
3
O
4
-ATPyHS@GO adsorbent was used for the
extraction of thallium in the water, wastewater and
the urine samples. The thallium concentration was
determined based on dispersive magnetic micro
solid-phase extraction by F-AAS.
2. Experimental
2.1. Apparatus and Characterization
absorption spectrometer coupled (F-AAS, Varian,
USA). The Air-acetylene (C
2
H
2
) and the deuterium
lampas was adjusted The limit of detection (LOD)
and sensitivity of F-AAS obtained 0.2 mg L
-1
and
0.15 mg L
-1
. The HCL of Tl was adjusted based on
catalog book with wavelength of 276.8 nm, slit of
0.5 nm and current of 10 mA. All samples injected
to F-AAS by auto- injector (0.5-3 mL). The working
range and linear range of AT-AAS were obtained
0.2-75 mg L
and 0.2- 15 mg L
, respectively. The
electrothermal atomic absorption spectrophotometer
(ET-AAS, Varian, USA) was used for validation of
thallium in urine and water samples. For suppress of
ionization in F-AAS, the reagent of KNO
3
or KCl
was used as a 2000 mg L
-1
The
pH was calculated by digital pH meter (Metrohm
744, Swiss). The different buffer of the acetate (PH
3–6) were used for adjusting pH. The ultra-sonication
(Grant, U.K) and the Sigma 3K30 magnetic
centrifuge (30.000 rpm, UK) was used. The natural
from Merck chemical Company. The Perkin Elmer
Spectrum spectrophotometer (65 FT-IR, USA) was
used for FT-IR spectra. The PRO X-ray diffractometer
was used for
emission scanning electron microscope (FE-SEM)
were prepared by SEM of Tescan Mira-3.
70
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
2.2. Materials
All reagents with analytical grade such as; the
thallium solution (Tl NO
3
), the acids and base
solutions (HNO
3
, HCl, NaOH) were purchased
from sigma Aldrich (Germany). The standard
solution of thallium nitrate (CAS N: 10102-45-1,
Sigma, Germany) was prepared from stock of 1000
mg L
-1
solution in 1 % HNO
3
for further studies.
The standard solutions for calibration were daily
prepared by distilled water (DW) from Millipore
(USA). The other reagents such as acetone and
ethanol with analytical grade were purchased from
Merck (Germany). The citric acid was used for
phosphate citrate buffer for PH between 2.1–7.4
and the acetate buffer was used for pH from 2.8 to
6.2 which was purchased from Merck.
2.3. Synthesis of Fe
3
O
4
-ATPyHS@GO
Hummers method. 5 g of graphite powder was
mixed with 250 mL of H
2
SO
4
and stirred for 24
h. Then, 30 g of KMnO
4
was gradually added to
[21]. Due to
previous studies, 4-aminothieno[2,3-d] pyrimidine-
2-thiol (10 g) was added to 150 mL of ethanol and
DW (1:1 v/v). Then, 180 mg of GO was added to
the resulted solution at 35
o
C. The H
3
PO
2
(50 mL, 50
wt%) was added to product and stirred for 90 min.
The product of ATPyHS@GO was washed and
dried by DW and oven, respectively. The magnetic
nanostructure was prepared by co-precipitation
of FeCl
2
·4H
2
O and FeCl
3
·6H
2
O, in the presence
of 4-Aminothieno[2,3-d] pyrimidine-2-thiol graft
on GO (ATPyHS@GO). First, the mixture of
FeCl
2
·4H
2
O and FeCl
3
·6H
2
O was prepared with
a molar ratio of 1:2. For synthesis nanomagnetic
adsorbent, 10 mg of 4-aminothieno[2,3-d]
pyrimidine-2-thiol grafted on graphene oxide
(ATPyHS@GO) was solved to 10 mL of DW and
sonicated for 40 min. Then 125 mg of FeCl
2
·4H
2
O
and 200 mg of FeCl
3
·6H
2
O in 10 mL of deionized
water were added to remain solution at 25
C. For
adjusting of pH=11, the ammonia solution was
added at 65
C. After 20 min stirring, the product
was cooled at 25
C. Finally, the black Fe
3
O
4
-
ATPyHS@GO was centrifuged at 4000 rpm for 50
min, washed for 10 times (DW) and dried at 70
C
based on vacuum accessory [22-24].
Fig.1. Synthesis of nanomagnetic ATPyHS@GO adsorbent by 4-aminothieno[2,3-d]
pyrimidine-2-thioland and Fe
3
O
4
on GO [22-24]
71
Thallium extraction by Fe
3
O
4
et al
2.4. Extraction Procedure
and standard samples (4 - 300 µg L
) were used
for separation and determination of thallium ions
at pH 4-6. Firstly, 25 mg of Fe
3
O
4
-ATPyHS@
GO added to water, urine and thallium standard
solution and the sample sonicated for 3.0 min at
pH=5. After sonication, the Tl ions was chemically
absorbed on thiol groups (ATPyHS) of Fe
3
O
4
-
ATPyHS@GO adsorbent (Tl
+
……:SH-ATPy @
GO) and then, settled down in bottom of magnetic
centrifuge conical tube. Then, the thallium ions
were back-extracted from Fe
3
O
4
-ATPyHS@
GO at basic pH with NaOH solution (0.1 M, 0.5
mL) and was simply separated by the external
magnetic accessory. Finally, the remain solution
was determined by FAAS after dilution with DW
up to 1 mL (Fig.2). The procedure was round for a
blank solution without thallium ions for ten times.
The analytical parameters showed in Table 1. The
recovery of thallium extraction was calculated
by the equation 1. The C
i
and C
f
are the primary
determined by F-AAS (n=10).
Recovery (%) = (C
i
-C
f
)/C
i
×100 (Eq.1)
Table 1. The analytical parameters for determination thallium in water and urine samples based on Fe
3
O
4
-
Parameters Values
Working pH 4-6
Amount of Fe
3
O
4
-ATPyHS@GO adsorbent (mg) 25
Sample volume of water (mL) 50
Volume of sample injection 1.0 mL
Linear range for water
working range for water
Mean RSD %, n=10
4.0-300 L
-1
4.0-1400 L
-1
1.8
LOD for water 0.9 L
-1
Preconcentration factor 50
Volume and concentration of NaOH 0.5 mL, 0.4 M
Shaking time 3.0 min
R
2
= 0.9997
Fig.2. The extraction procedure of thallium in water and urine samples based
on Fe
3
O
4
-ATPyHS@GO adsorbent by
72
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
3. Results and Discussion
3.1. TEM Spectra
The TEM of Fe
3
O
4
-ATPyHS@GO and GO
adsorbent was prepared (Fig. 3a and 3b). Based on
the TEM images, both of GO and Fe
3
O
4
-ATPyHS@
GO have the thin sheets about 30-80 nm. The Fe
3
O
4
was seen as black point on surface of GO in TEM
of Fe
3
O
4
-ATPyHS@GO adsorbent (Fig. 3a).
3.2. FE-SEM Spectra
The morphology of Fe
3
O
4
-ATPyHS@GO and GO
electron microscopy (FE-SEM) (Fig. 4a and 4b).
Based on the SEM images, both of GO and Fe
3
O
4
-
ATPyHS@GO have the thin sheets nearly related to
each other. The SEM images of GO and Fe
3
O
4
@4-
PhMT-GO showed us, the HS and Fe
3
O
4
had no
effect on the morphology of the GO sheets. Also, the
nanoparticles of Fe
3
O
4
have a spherical morphology
on HS-GO with a diameter of 40 nm.
3.3. FTIR diagram
The infrared spectra of pure GO and Fe
3
O
4
-
ATPyHS@GO are presented in Figure 5.
The spectra of GO and Fe
3
O
4
-ATPyHS@GO
are showed to the stretching bands of (O-H;
Fig. 3a. TEM of the Fe
3
O
4
-ATPyHS@GO Fig. 3b. TEM of the GO adsorbent
Fig. 4a. FE-SEM of the Fe
3
O
4
-ATPyHS@GO
Fig. 4b. FE-SEM of the GO
73
Thallium extraction by Fe
3
O
4
et al
3415), (C=O; 1730), (C=C; 1624), and (C-O;
1061). Also, the peak of FTIR at range of 2600-
3500 cm
-1
belong to to the O-H and C=C(OH)
function. Moreover, the peak of 1400 cm
-1
and
2234 cm
-1
related to tertiary hydroxyl groups(OH)
and HS function on GO.
In –addition the peaks
at 628 cm
-1
and 583 cm
-1
belong to the Iron oxide
[22-24].
3.4. X-ray diffraction (XRD) patterns
The X-ray diffraction patterns of Fe
3
O
4
-ATPyHS@
GO was shown in Figure 6. GO have a single
O
2
groups. In both of GO and Fe
3
O
4
@4-PhMT-
GO adsorbent, the XRD peaks were observed at
o
which are belonged to (002)
and (100), respectively. Based on the XRD peak of
Fe
3
O
4
-ATPyHS@GO, the intensity of the peak at
HS and Fe
3
O
4
o
showed that the stability of O
2
functionalities even
after the functionalization of GO with HS or Fe
3
O
4
groups. The similar XRD peak of Fe
3
O
4
can be
seen for the Fe
3
O
4
-ATPyHS@GO adsorbent which
of Fe
3
O
4
. So, the functionalities of HS and Fe
3
O
4
were successfully done without changing in
structure of GO.
Fig. 5. The FTIR spectra of pure GO and Fe
3
O
4
-ATPyHS@GO adsorbents
Fig. 6. XRD patterns of (a) GO adsorbent and (b) Fe
3
O
4
-ATPyHS@GO adsorbent [22]
74
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
3.5. Optimizing extraction parameters
of thallium in water, wastewater and urine samples
was achieved by a novel Fe
3
O
4
-ATPyHS@
thallium
thallium based on Fe
3
O
4
-ATPyHS@GO adsorbent,
the extraction conditions must be optimized. So,
the effective parameters such as pH, the amount of
adsorbent, the eluent, the sample volume, and the
adsorption capacity must be studied.
3.5.1. pH effect
The pH of extraction of thallium in water and urine
samples must be evaluated and optimized. The favorite
pH cause to increase the adsorption of thallium ions
by the Fe
3
O
4
-ATPyHS@GO adsorbent. So, the
different pH between 2-11 was examined for thallium
extraction in water and urine samples by adjusting pH
with different buffer solutions. The results showed us,
the maximum extraction of the Fe
3
O
4
-ATPyHS@GO
adsorbent for Tl(I) was obtained at pH of 4-7. Also, the
recoveries for thallium were decreased at acidic pH
less than 4 and basic pH more than 7. So, the pH 5 was
selected as the optimal pH for extraction of thallium
in water and urine samples by the Fe
3
O
4
-ATPyHS@
GO adsorbent (Fig.7). The mechanism of extraction
of thallium was occurred by the dative bond of thiol
group [2(Ti
+
) ……..
2
:SH-ATPyHS@GO- Fe
3
O
4
) with
the positively charged of thallium(Tl
+
) at optimized
pH. In addition, the thallium ions participated
(Tl(OH)) at more than pH 7.5.
3.5.2. Amount of Fe
3
O
4
-ATPyHS@GO adsorbent
Foe high extraction of thallium in water/urine
samples, the amount of the Fe
3
O
4
-ATPyHS@
GO adsorbent evaluated at thallium concentration
. For this purpose, the various
amount of the Fe
3
O
4
-ATPyHS@GO adsorbent
between 5-50 mg were studied for Tl(I) extraction
method. As Figure 8, the best recovery for thallium
extraction was created by 20 mg of Fe
3
O
4
-ATPyHS@
GO adsorbent. So, 25 mg of the Fe
3
O
4
-ATPyHS@
GO adsorbent was used for further work.
3.5.3. Effect of eluents
The various eluents such as HNO
3
, H
2
SO
4
, NaOH
and CH
3
COOH were used for back extraction
thallium ions from the Fe
3
O
4
-ATPyHS@GO
adsorbent. In acidic and basic pH, the dative
bonding between the thiol group (HS) and thallium
(Tl) was started to dissociate (4>pH>6). So, after
break down the bonging, the thallium ions released
in eluent solution by elution. At pH more than 7, the
thallium participated as thallium hydroxyl (Tl-OH)
Fig.7. The effect of pH on thallium extraction in water and urine samples
by Fe
3
O
4
-ATPyHS@GO adsorbent
2 3 4 4.5 5 5.5 6 6.5 7 8 9
75
Thallium extraction by Fe
3
O
4
et al
and in low pH, the bonding of Tl-SH dissociated.
Due to results, the HNO
3
and NaOH has more
recovery as compared to H
2
SO
4
and CH
3
COOH.
The different acid solution with different volume
and concentration was used for back extraction Tl(I)
in water and urine samples (0.2-2.0 mol L
-1
, 0.1-0.5
the Tl ions were completely back-extracted from the
Fe
3
O
4
-ATPyHS@GO adsorbent by nitric acid and
NaOH solutions more than 1.0 mol L
-1
and 0.1 mol
L
-1
, respectively. Therefore, 0.1 mol L
-1
of NaOH
was used as an optimum eluent for this study. Also,
the effect of different volumes of eluents from 0.1
mL to 0.5 mL for thallium was checked. Therefore,
0.5 mL of NaOH (0.1 M) selected as optimum
elution (Fig. 9). Also, the more concentration of
NaOH (M>0.2) caused to the thallium participation
(Tl-OH).
0.1 0.2 0.3 0.5 1 1.5 2
Fig.9. The effect of eluent concentration on thallium extraction
in water and urine samples by the Fe
3
O
4
-ATPyHS@GO adsorbent
Fig.8. The effect of amount of Fe
3
O
4
-ATPyHS@GO adsorbent on thallium extraction in water
5 10 15 20 25 30 35 40 50
76
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
3.5.4.Effect of sample volume
water/urine samples is sample volume. The effect of
different volumes between 10-200 mL for Tl extraction
based on the Fe
3
O
4
-ATPyHS@GO adsorbent was
studied and optimized in water and urine samples (4-
). By results, the high recovery (%) was
occurred for 55 mL for urine and 70 mL for water
samples. So, 50 mL of sample volume was used for
(Fig. 10).
3.5.5. Effect of sonication time
The dispersion of Fe
3
O
4
-ATPyHS@GO adsorbent
increased the interaction between thiol group (HS) and
thallium ions at pH 5. By uniform dispersion of the Fe
3
O
4
-
ATPyHS@GO adsorbent, the chemical adsorption of
thallium occurred. Therefore, the extraction recovery
increased due to physical adsorption of GO and
chemical bonding of HS group in Fe
3
O
4
-ATPyHS@GO
adsorbent. Moreover, the sonication times was effected
on extraction rate. The various sonication times (1-10
minute) was used and the recoveries obtained. The
best recoveries were achieved at the sonication time of
2.5 min. Therefore, 3.0 min was used as the optimum
time for thallium extraction in water and urine samples.
After sonication, the magnetic adsorbent (Tl- Fe
3
O
4
-
ATPyHS@GO) was collected from the liquid samples
by extra magnet accessory.
3.5.6. The adsorption capacity
The Fe
3
O
4
-ATPyHS@GO adsorbent was dispersed in
water samples and the extractions of thallium ions from
liquid samples were followed many times and re-usage
of adsorbent calculated. The results showed, the Fe
3
O
4
-
ATPyHS@GO adsorbent can be used for 18 extraction
cycles at pH of 5.0. The absorption capacities (AC)
of the Fe
3
O
4
-ATPyHS@GO adsorbent depended on
the BET, the function group and size of adsorbent.
In batch system, 25 mg of the Fe
3
O
4
-ATPyHS@
GO
nanoparticles
was used in 50 mL of thallium
solution (5 mg L
-1
; ppm) at pH 5.0. After 10 minutes’
sonication, the AC of adsorbent calculated by F-AAS.
The adsorption capacities of the Fe
3
O
4
-ATPyHS@GO
adsorbent for Tl ions were obtained 137.5 mg g
-1
.
3.5.7. Interference of coexisting ions
The effect of main coexisting ions on thallium extraction
based on the Fe
3
O
4
-ATPyHS@GO adsorbent was
SPE procedure. So, the effect of various concentrations
of interfering ions (1-3 ppm) was studied for 50 mL
of water samples by proposed procedure at pH 5.0.
The main concomitant ions in water and urine were
selected and used for thallium extraction by the Fe
3
O
4
-
ATPyHS@GO adsorbent. The results showed that
the interference coexisting ions do not affect on the
thallium extraction in optimum conditions (Table 2).
Fig.10. The effect of sample volume on thallium extraction in water and urine samples
by the Fe
3
O
4
-ATPyHS@GO adsorbent
10 20 40 50 60 80 100 200
77
Thallium extraction by Fe
3
O
4
et al
3.5.8. Validation in real samples
and determination of thallium in water and urine
samples. The validation of results for the Fe
3
O
4
-
ATPyHS@GO adsorbent were shown in Table 3. For
validation, the real samples were spiked to different
concentration of standard solutions of thallium and
pH 5.0 (Table 3)
and high recovery for thallium ions were obtained
in water and human urine samples by nanoparticles
of the Fe
3
O
4
-ATPyHS@GO adsorbent. Moreover,
the standard reference materials were prepared in
water and urine samples with ICP-MS analyzer for
Fe
3
O
4
-ATPyHS@GO adsorbent (Table 4).
Table 3. Validation of methodology for thallium ions in water and urine samples based
on Fe
3
O
4
-ATPyHS@GO adsorbent by spiking of real samples
Sample* Added
(μg L
-1
)
*
Found (μg L
-1
) Recovery (%)
a
Well water
--- 56.4 ± 2.4 ---
50 104.6 ± 4.5 96.4
b
Wastewater
--- 146.6 ± ---
150 294.3 ± 13.4 98.5
Wastewater
c
--- 122.9 ± 5.9 ---
100 225.7 ± 11.2 102.8
Urine
--- 4.7 ± 0.2 ---
5 9.6 ± 0.5 98.0
Urine
--- 11.9 ± 0.4 ---
10 21.6 ± 0.9 97.0
--- 28.9± 1.3 ---
Urine 30 59.8± 2.7 103
a
Well water prepared from Varamin garden, Tehran,Iran
b
Wastewater prepared from chemical factory, Karaj, Iran
c
Wastewater prepared from petrochemical factory, Arak, Iran
Urine prepared from workers from car, chemical and paint factories, Iran
Table 2.
SPE procedure
Interferences ions
Mean ratio
(C
I
/C
Tl(I)
)
Mean ratio
(C
I
/C
Tl (I)
)
Recovery (%) Recovery (%)
Urine Water Urine Water
Mo
2+
, Ni
2+
, Co
2+
, Mn
2+
400 650 98.1 97.0
Zn
2+
, Cu
2+
700 900 96.5 98.3
Pb
2+
, Cd
2+
, V
3+
, Cr
3+
550 700 98.6 99.2
Br
-
, F
-
, Cl
-
, I
-
, NO
3
-
900 1200 97.9 98.5
Na
+
, K
+
, Ca
2+
, Mg
2+
1000 1300 97.3 98.8
Se
4+
350 400 97.1 97.6
Al
3+
, Be
+2
600 600 97.4 98.7
CO
3
2-
, PO
4
3-
, SO
4
2-
, NH
4
+
800 950 97.7 98.6
Hg
2
, Ag
+
200 300 96.8 97.4
Sn
2+
500 700 98.2 97.9
78
Anal. Methods Environ. Chem. J. 4 (3) (2021) 68-79
4. Conclusions
A simple and reliable method was used for
preconcentration, separation and determination
of Tl (I) in human urine and water samples by
was developed based on magnetic Fe
3
O
4
-
ATPyHS@GO adsorbent at pH 5.0 without any
organic chelating agent and organic solutions.
The proposed method based on the Fe
3
O
4
-
ATPyHS@GO adsorbent can be considered for Tl
reusability and fast separation phase. The newly
developed method was low interference, easy
usage for sample preparation in human urine
samples and also provides low LOD (0.9 µg L
),
RSD (1.8-2.1%) values as well as good PF (50)
and quantitative recoveries more than 95% for
thallium extraction in water and urine human
matrixes. So, the proposed method based on
magnetic nanoparticles and thiol groups on the
Fe
3
O
4
-ATPyHS@GO adsorbent can be considered
as a fast sample preparation technique with low
amount of adsorbent for thallium separation and
determination by F-AAS.
5. Acknowledgements
The authors wish to thank the Department of
Chemistry, Shahid Bahonar University of Kerman,
Kerman, Iran and Department of Chemistry of
Islamic Azad University, Kerman, Iran.
6. References
[1] T.S. Lin, J.O. Nriagu, Thallium in the
environment, New York: Wiley, pp.31-44,1998.
[2 ] C. Yang, Y. Chen, P. Peng, X. Chang, C. Xie,
Distribution of natural and anthropogenic thallium
in the soils in an industrial pyrite slag disposing
area, Sci. Total Environ., 341 (2005) 159–172.
Thallium contamination of soils/vegetation
as affected by sphalerite weathering: a
model rhizospheric experiment, J. Hazard.
Mater., 283 (2015) 148–156. https://doi.
org/10.1016/j. jhazmat.2014.09.018.
of speciation analysis of thallium in plants,
Chemosphere, 144 (2016) 1216–1223.
[5] Z. Ning, L. He, T. Xiao, L. Márton, High
accumulation and subcellular distribution of
thallium in green cabbage, Int. J. Phytoremed.,
17 (2015)1097–1104.
[6] B. Krasnodebska-Ostrega, Tl I and Tl III
presence in suspended particulate matter:
speciation analysis of thallium in wastewater,
Environ. Chem., 12 (2015) 374–379.
[7] P. Cvjetko, I. Cvjetko, M. Pavlica, Thallium
toxicity in humans, Arch. Ind. Hyg.
Toxicol., 61 (2010) 111–119. https://doi.org/
10.2478/10004-1254-61-2010-1976.
Table 4. Validation of
Recovery (%)
Found
*
( μg L
-1
)
Added
ICP-MS ( μg L
-1
)
Sample
-----24.9 ± 1.2-----25.3 ± 0.5CRM1
97.044.3 ± 1.920.0
-----64.1 ± 2.8-----62.7 ± 0.7CRM 2
98.2113.2 ± 5.250.0
-----4.8 ± 0.2-----5.1± 0.2CRM 3
1029.9 ± 0.45.0
-----6.2 ± 0.3-----6.4 ± 0.2CRM 4
96.011.0± 0.55.0
*
-1
)
-1
)
-1
)
-1
)
79
Thallium extraction by Fe
3
O
4
et al
[8] J.M. Wallace, Kale and thallium: insights
from your nutrition team. Permaculture
solutions for healing, 2015.
[9] A. Lansdown, The carcinogenicity of
metals: human risk through occupational and
environmental exposure, Cambridge: Royal
Society of Chemistry, pp. 323–330, 2013.
[10] Z. Groesslova, A. Vanek, M. Mihaljevic,
V. Ettler, M. Hojdovác, T. Zádorováa,
Bioaccumulation of thallium in a neutral
soil as affected by solid-phase association, J.
Geochem. Explor., 159 (2015) 208–212.
[11] T. Wojtkowiak, B. Karbowska, W.
Zembrzuski, M. Siepak, Z. Lukaszewski,
source of thallium in the environment, J.
Geochem. Explor., 161 (2016) 42–48. https://
doi.org/10.1016/j. gexplo.2015.09.014.
[12] F.S. Hussain, N.S. Hussain, Clinical utility
of thallium-201 single photon emission
computed tomography and cerebrospinal
polymerase chain reaction in the diagnosis of
AIDS-related primary central nervous system
lymphoma, Cureus., 8 (2016) e606.
[13] L. Osorio-Rico A. Santamaria S. Galván-Arzate,
Thallium toxicity: general issues, neurological
symptoms, and neurotoxic mechanisms, Adv.
Neurobiol., 18 (2017) 345-353.
[14] V. Yu, M. Juhász, A. Chiang, N. Atanaskova
Mesinkovska, Alopecia and associated toxic
agents: A systematic review, Skin Appendage
Disord., 4 (2018) 245-260.
[15] HY. Yu, C. Chang, F. Li, Q. Wang, M. Chen,
and lettuce: Potential health risks for local
residents of the Pearl River Delta, South
China, Environ. Pollut., 241 (2018) 626-635.
for ultrasensitive determination of bismuth
based on hydride generation – the role of
993-1002.
monitoring of total thallium in grain products, Int.
J. Environ. Res. Public Health, 15 (2018) 653.
[18] L. Nyaba, T. S. Munonde, Magnetic Fe
3
O
4
@
Mg/Al-layered double hydroxide adsorbent
for preconcentration of trace metals in water
matrices, Sci. Reports, 11(2021) 2302.
[19] L. Nyaba, B. Dubazana, A. Mpupa, P. N.
Nomngongo, Development of ultrasound-
assisted dispersive solid-phase microextraction
based on mesoporous carbon coated with
silica@iron oxide nanocomposite for
preconcentration of Te and Tl in natural water
systems, Open Chem., 18 (2020) 412–425.
[20] T. Kusutaki, M. Furukawa, Preconcentration of
Pb with aminosilanized Fe
3
O
4
nanopowders in
environmental water followed by electrothermal
atomic absorption spectrometric determination,
Chem. Eng., 3 ( 2019) 74.
[20] W.S.J. Hummers, R.E. Offeman, Preparation of
graphitic oxide, J. Am. Chem. Soc., 80 (1958) 1339.
[21] S. Khodabakhshi, F. Marahel, A. Rashidi, M.
Khaleghi Abbasabadi, A green synthesis of
substituted coumarins using nano graphene
oxide as recyclable catalyst, J. Chin. Chem.
Soc., 62 (2015) 389-392.
[22] H. Shirkhanloo, M. K. Abbasabadi, F. Hosseini,
methanethiol nanomagnetic composite for rapid
separation of aluminum in wastewaters, foods,
and vegetable samples by microwave dispersive
magnetic micro solid-phase extraction, Food
Chem., 347 (2021) 129042.
[23] M.K. Abbasabadi, A. Rashidi, S. Khodabakhshi,
Benzenesulfonic acid-grafted graphene as a new
removal, J. Nat. Gas Sci. Eng., 28 (2016) 87-94.
[24] M. Khaleghi-Abbasabadi, D. Azarifar,
Magnetic Fe
3
O
4
-supported sulfonic acid-
functionalized graphene oxide (Fe
3
O
4
@GO-
naphthalene-SO
3
H): a novel and recyclable
nanocatalyst for green one-pot synthesis, Res.
Chem. Intermed., 45 (2019) 2095-2118.
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Effects of air, water and land dumpsite on human health and
analytical methods for determination of pollutants
Ihenetu Stanley Chukwuemeka
a,*
, Victor Obinna Njoku
a
, Chinweuba Arinze
b
,
Ibe Francis Chizoruo
a
, and Ekeoma Nmesoma Blessing
C
a
Chemistry Department, Imo State University Owerri, Imo State Nigeria
b
Chemistry Department, Chukwuemeka odimegwu Ojukwu University Uli, Anambra Nigeria
C
Medicine and surgery Department, Gregory University, Uturu Abia State, Nigeria
ABSTRACT
Environment pollutants are found here and there in developing
countries and these contaminations affect the environment adversely.
This is done by peculation of solid and liquid substances in the
dumpsites and industrial pollutions into the soil which form toxic
chemicals as well as evaporation of gases into the atmosphere. Few
remediation of pollution which includes incineration which is the
waste treatment process that involves the combustion of organic
substances contained in waste material, the waste handling practices,
the recycling resource recovery, the avoidance and reduction methods,
the adsorption based on nanotechnology and the bioremediation
technology which appears as a cost-effective and environmental
friendly approach for cleanup. Recently researches shows that various
chemicals (VOCs, BTEX, heavy metals) that might be delivered
into the air or water can cause unfriendly health effects which was
analyzed based on sample treatments (solid phase extraction: SPE,
the liquid-liquid microextraction: LLME, the magnetic solid phase
extraction: MSPE) and instruments such as ET-AAS, F-AAS and
GC-FID methods. The related weight of disease can be substantial,
and interest in research on health effects and intervention in explicit
development of control systems. Pollution control and determination
and analytical chemistry specialists need to foster associations with
different areas to recognize and carry out need interventions.
Keywords:
Environment pollutants,
Water,
Air and soil,
Analytical chemistry methods,
Human health
ARTICLE INFO:
Received 26 May 2021
Revised form 28 Jul 2021
Accepted 21 Aug 2021
Available online 30 Sep 2021
*Corresponding Author: Ihenetu Stanley Chukwuemeka
Email: Ihenetustanley@yahoo.com
https://doi.org/10.24200/amecj.v4.i03.147
------------------------
1. Introduction
The environment pollution in waters and the
dumpsite in soil can be described as a portion of
land where waste materials and discarded. In Africa,
thousands and tons of wastes are generated daily in
many ways [1]. The indiscriminate and unprotected
disposal of waste can instigate environmental
degradation through introducing various toxicants,
including heavy metals in the soil, air and water.
Open dumping of municipal solid waste is a
common practice in Nigeria. Chemical industries
and dumpsites are important pollution sources
in the environment (VOCs and heavy metals,
organic and inorganic pollutants, toxic gas, organic
cells, viruses) and can cause various diseases in
the human body. Traditionally, dumpsites have
remained the utmost regular method of waste
dumping in many places around the world both in
81
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
urban and rural areas. Most of the dumpsites are
situated within the locality of living communities
and wetlands. Some of chemical factories, oil
company and petrochemical industries are located
close to rivers, well waters, the agricultural soil
where human activities are carried out [1]. In
addition, the environmental pollutants must be
removed from wastewater, water and air based on
nanosorbents by chemical and physical adsorption
process.
strong or holder of vaporous material [2]. Recently,
the different adsorbent based on nanotechnology
have positive effected on decreasing of pollutants
from environment matrixes.
2. Environment pollutions
2.1. VOCs and heavy metal pollutions in water,
soil, air
Volatile organic compounds (VOCs) are
compounds that have a high vapor pressure and
low water solubility. Numerous VOCs are human-
made chemicals that are utilized and delivered in
the assembling of paints, drugs, and refrigerants
[3]. VOCs regularly are organic solvents, like
trichloroethylene; fuel oxygenates, for example,
methyl tert-butyl ether (MTBE); or side-effects
delivered by chlorination in water treatment, like
chloroform. VOCs are regularly parts of petrol
fuels, pressure driven liquids, acetones, and
cleaning specialists. VOCs are shared conviction
water impurities. Volatile organic compounds
(VOCs) are emitted as gases from certain solids or
liquids. VOCs include a variety of chemicals, some
of which may have short- and long-term adverse
health effects. Concentrations of many VOCs are
consistently higher indoors (up to ten times higher)
than outdoors [4]. VOCs are emitted by a wide
array of products numbering in the thousands.
Examples include: paints and lacquers, paint
strippers, cleaning supplies, pesticides, building
carbonless copy paper, graphics and craft materials
including glues and adhesives, permanent markers,
and photographic solutions [3-4]. A heavy metal is
cm
-3
The water treatment of explosive and heavy metals
co-contaminated soil was evaluated [5]. According
to previous references, the expression of heavy
metals is frequently utilized as a gathering name
for metals and semimetals (metalloids) that have
been related with pollution and potential toxicity or
ecotoxicity [6]. Very as of late, we have proposed
metals have been characterized (natural occurring
metals having atomic number more prominent than
20 and an essential density more noteworthy than
3
). Also, determination of heavy metals in
soil, vegetables and wastewater based on DLLME
coupled to GFAAS [6]. Heavy metal harmfulness
can have a few health impacts in the body. Heavy
metals can harm and modify the working of organs
like the brain, kidney, lungs, liver, and blood.
Heavy metal harmfulness can either be acute or
chronic impacts. Long haul openness of the body
to heavy metal can dynamically prompt solid,
physical and neurological degenerative cycles that
are like diseases like Parkinson’s disease, different
sclerosis, strong dystrophy and Alzheimer’s
disease. Likewise, chronic long haul openness
of some heavy metals might cause cancer [7].
Many different analytical procedures and sample
preparation have been reported for VOCs and heavy
metal analysis in water and human samples. The
liquid-liquid extraction (LLE), supported liquid
extraction (SLE), and solid-phase extraction (SPE)
have existed for decades and if you’re doing organic
sample preparation, you’re probably quite familiar
with at least one of these techniques [8]. The micro
solid-phase extraction (MSPE) and dispersive SPE
is a technique which separates analytes, using
physical or chemical adsorption interactions with
a solid media. The media is mounted on a sorbent
material in the form of either a disk or cartridge.
The analytes are absorbed on the media as the
sample passes through the sorbent material such
as zeolites, silica (MSN.MCM), CNTs (MWCNTs,
SWCNTs), graphene (NG, NGO, NG-COOH)
82
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
and MOF. The analytes are then eluted from the
media using a solvent (HNO
3
, NaOH) in which the
analytes are soluble and this solution is retained for
analysis before determination by F-AAS, ET-AAS,
GC-FID, GC-Mass and the UV-Vis spectrometry
[8]. SPE is one of the most widely used sample
preparation techniques. In SPE, an aqueous sample
is passed through a short column containing a
suitable solid sorbent, and the solutes are adsorbed
onto the column. Afterwards, small amounts of
organic solvents of high elution strength are used to
recover the analytes from the sorbent, which leads
to their enrichment [9]. Solid phase extraction
utilizes small amounts of solvent and generates little
waste. As a result, it is considered an ecofriendly
technique. SPME was introduced by Ayotamuno
at al [10]. According to the GAC guidelines, it is
a green extraction procedure because it avoids the
use of organic solvents and combines extraction,
enrichment and sample injection into a single step.
Analytes partition between the sample matrix and
directly in the sample (direct immersion, or DI-
SPME), or between the sample headspace and the
above the BTEX sample (HS-SPME/GC-FID)
[10]. Partitioning continues until equilibrium is
established between all phases involved. When the
is transferred directly to the analytical instrument
of choice, typically a gas chromatograph, where
analyte desorption takes place. The major
advantages of SPME include low cost, simplicity,
elimination of the solvent disposal costs, short
sample preparation time, reliability, sensitivity,
and selectivity [11]. Liquid-liquid extraction (LLE)
uses huge volumes of solvents that are regularly
risky according to an environmental viewpoint and
the cycle is dreary and tedious. During the previous
decade, this method has gone through a dynamite
change with regards to high-throughput screening
with the presentation of miniaturized conventions
is the utilization of the 96-well plate design related
to a liquid dealing with robotic framework; it
follows a similar standard as mass scale LLE [12].
2.2. Environment pollution and human health
Effects of environment pollutants and
disproportionate dumpsite on human health
is overwhelming and numerous to mention,
especially in developing cities with the high
range and production of plastic materials all over
the place. All dumpsite is inclined to discharge
pollutants to immediate water bodies and to
the air by way of leachates and dumpsite gases
correspondingly. Industrialization, population
growth and unplanned urbanization have partially
or totally turned our environment to dumping sites
for waste materials. As many water resources have
other living systems as a result of indiscriminate
dumping of refuse. In Nigeria, contamination and
by solid wastes is under disseminate thereby
making them inappropriate for man’s use [13] As
highly populous areas in most developing and
underdeveloped countries owing to the cost and
lack of implementation of pertinent enactment. Poor
regional and urban planning, lack of implementation
of pertinent laws and announcements on waste
role to the occurrence of dumpsites within people’s
inhabitations in developing countries. The surface
run off and leachates from dumpsites are sources
of fresh water contamination. The danger pose by
leachates from metropolitan dumpsites depends
on the waste conformation, amount, life span
and time, temperature, moisture, obtainability for
oxygen, soil morphology, and the comparative
distance of the locations to the living community
and water body. The pollution of soil with heavy
to have possible impact on environmental quality
and human health as well as professing a long
term danger to groundwater and ecosystems
[14]
contain a wide range of metals. Source of these
83
heavy metals ranges from industrial to municipal
generation, automobiles, agricultural and domestic
practices. The conventional credence that wastes
are occasionally hazardous to health cannot be
overemphasized. Hazardous waste can cause and
has caused pollution, damage to health and even
death. Exposure to multiple chemical combinations
in populations living near waste dump sites has led
to series of human health disorders. It has been
reported that heavy metals, VOCs and anions in
dump sites leachates can initiate chromosomal
sites are disposed to mutagenic effects. The degree
of contamination growing from percolation of
leachates is established by a number of components
that include the physicochemical properties of the
leachates and soil and the hydrological condition of
the surrounding location [15].
2.3. Wastewater pollution
There are four main treatment steps in the
wastewater treatment process. The preliminary
treatment removes all large and settleable solids
from the wastewater. Secondary treatments use
accelerated microbiological growth to remove
organic pollutants. The tertiary treatment utilizes a
combination of chemical and biological processes
to reduce nutrient loading in the wastewater.
The quaternary treatment removes particularly
compounds or other complex molecules which was
used by different organic and inorganic adsorbents
such as silica (MSN.MCM) and ionic liquids(ILs).
Analytical testing based on instruments at each step
is required to monitor key chemical parameters like
the nitrogen compounds, the malondialdehyde, the
formaldehyde, the phosphates, and the chlorine
[16]. Monitoring silicate, calcium, and magnesium
content is imperative as they form scale deposits,
leading to higher maintenance costs and downtime
which was determined as mg L
-1
with atomic
absorption spectrometry (FAAS, ETAAS). As the
primary treatment, the treatment of wastewater
by a physical or potentially chemical interaction
including settlement of suspended solids, or
other cycle in which the Biological Oxygen
Demand (BOD) of the approaching wastewater is
decreased by essentially 20% before release, and
the total suspended solids content is diminished by
basically half. The secondary treatment followed
with the post-primary treatment of wastewater by
an interaction by and large including biological
or other treatment with a secondary settlement or
other cycle, bringing about a BOD reduction of
basically 70% and the Chemical Oxygen Demand
(COD) reduction of essentially 75% [17]. Due
to the tertiary treatment of public wastewater, the
treatment of nitrogen or potentially phosphorus,
the nature of a particular utilization of water was
evaluated (the microbiological pollution and
shading). For organic pollution, the treatment
are the accompanying: organic pollution reduction
of essentially 95% for BOD, 85% for COD,
the nitrogen reduction of essentially 70%, the
phosphorus reduction of essentially 80% and the
microbiological reduction accomplishing a waste
coliform thickness of < 1000 of every 100 ml.
extra treatment for explicit determinants that may
not be normal in many wastewaters [18,19].
2.4. Environment pollution sources
natural surface or underground water (domestic
waste water, industrial, nitrates from fertilizer) or
soil (with fertilizers, pesticides, radioactive wastes,
etc.). Presently, about 82% of lands are polluted by
the products of petroleum source (hydrocarbons,
solvents etc.) used as an energy foundation in the
oil industry, in addition, the chemicals were used
in various industries and their wastewaters may be
included the different pollutants such as, BTEX,
VOCs, mercury, arsenic, nickel and vanadium
which was determined by analytical methods [19].
bodies, air, soil and subsoil, such as fuel and oil
products, crude oil, hydrocarbon residues, other
products resulting from the operation (unsaturated
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
84
and saturated aliphatic hydrocarbons, and the
polycyclic and monocyclic aromatic). It also stances
risks to human health, biological environment
and vegetation, aromatic compounds having a
strong attribute of carcinogenic and mutagenic
basement of various buildings [20]. Accidental oil
pollution has turn out to be a common phenomenon
nowadays that can cause environmental and social
disasters. Potential causes of direct pollution
of soil and subsoil can be enclosed by tanks,
separators old from wastewater treatment plants,
underground pipelines, slurries, settling basins and
waste pits of tar, ramp CF loading and unloading,
sewerage networks etc. Solid residues, unstored
corresponding, which can contaminate the soil,
come from: solid impurities concerned in crude oil,
sewage sludge from different wastewater treatment
plants, solid waste from cleaning of incinerator ash
sludge and the maintenance, powder catalyst. Most
oil pollution sources come from anthropogenic
sources, but there are also some natural sources that
pollute the soil and the water bodies [20]. Dumpsite
generally contaminates the immediate environment
where they are found and they carry hazardous
organisms which affects both the environment and
the inhabitants of this environment where they are
found on. Dumpsite causes various diseases and it
increases air borne diseases as well [21].
2.5. Soil pollution
Soil pollution is the change in the composition of
soil properties is different characteristics. It involves
the building up of toxic persistent substances,
slats, radioactive materials, toxic chemicals and
other disease causing agents in the soil which have
adverse effects on the soil and probably has an
adverse effect on plant growth and animal health.
Soil comprises of a solid phase (organic matter and
minerals matter) as well as an absorbent phase that
grasps gases and water [22]. Soil is the mixture of
minerals, organic matter, gases, liquids, and the
countless organisms that together support life on
earth [22]. The organic portion, which is obtained
from the decayed remnants of plants and animals,
is concentrated in the dark topmost topsoil. The
inorganic fraction made up of rock fragments, was
formed over thousands of years by physical and
chemical weathering of bedrock. Productive soils
are indispensable for agriculture to furnish the
world with adequate food. In a general wisdom, soil
chemicals (pollutants or contaminants) in soil in
extreme enough concentrations to be of danger to
human health and the ecosystem. In additionally,
yet when the levels of contaminants in soil are
not of peril, soil pollution may take place simply
due to the fact that the levels of the contaminants
in soil surpass the levels that are naturally present
in soil (in the situation of contaminants which
occur naturally in soil). Soil pollutants comprise
a large variability of contaminants or chemicals
(organic and inorganic), which may possibly be
both naturally- occurring in soil and man-made.
In both cases, the main soil pollution instigates
are the human activities which might be leaks and
spilling of oil, manufacturing process and dumping
of toxic materials and substances in the soil [23].
The heavy metals in soil were determined by the
Atomic Absorption Spectrophotometer (AAS,
Perkin Elmer 2380) [24]. The Analytical methods
for removal VOCs and heavy metals from soil were
used by different methodology (Figure 1-3).
2.5.1. In situ soil vapour extraction
Volatile and some semi-volatile organic compounds
(VOCs and Semi-VOCs) can be eliminated from
unsaturated soils by a cycle known as soil vapor
extraction (SVE). SVE as an in situ tidy up measure
permits contaminated soil to be remediated without
[25]. Soil
vapor extraction (SVE) is an in situ unsaturated
(vadose) zone soil remediation technology in
which a vacuum is applied to the soil to induce the
controlled progression of air and eliminate volatile
and some semi-volatile contaminants from the
soil. The gas leaving the soil might be blessed to
receive recuperate or obliterate the contaminants.
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
85
Fig. 1. Remediation of heavy metal contaminated soil
by asymmetrical alternating current electrochemistry [28]
The disadvantage in the utilization of SVE for
remediation of contaminated site is that SVE
cannot eliminate heavy oils, metals, PCBs, or
dioxins from contaminated soil; it is just powerful
for remediation of soil contaminated with VOCs
and Semi-VOCs. Since the interaction involves
the continuous progression of air through the soil,
notwithstanding, it regularly advances the in situ
biodegradation of low volatility organic compounds
that might be available [26].
2.5.2. Excavation
Excavation (evacuation) is a crucial remediation
strategy including the expulsion of debased soil/
media, which can be dispatched off-site for
treatment and additionally removal, or treated
nearby when pollutants are manageable to solid
remediation procedures [26]. Bioremediation is
one of the most viable options for remediating soil
contaminated by organic and inorganic compounds
considered detrimental to environmental health
[27].
2.5.3.bioremediation strategy and digestion
process (Determination in soil)
Biostimulation of indigenous microbes is
a bioremediation strategy mostly used for
remediation of contaminated soil. This involves
addition of nutrients, either organic or inorganic, to
enhance the activities of indigenous microbes [27].
The soil sample was digested with HNO
3
/H
2
O
2
by
micro wave accessory. At 200
o
C/ UV irradiation,
the sample digested and organic compound convert
to SOx and NOx and COx and exit as gas from
head of microwave tube under hood conditions.
The inorganic compounds determined in remained
solution by FAAS. Also by headspace microwave,
the VOCs extracted by new technique and online
determined by GC-FID.
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
86
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
Fig.2. Biological-based methods for the removal
of volatile organic compounds (VOCs) and heavy metals
Fig.3. Microwave digestion methods for determination heavy metals and VOCs in soil
87
3. Soil Pollutants, Analysis and Health
Effect
3.1. Soil pollutant
There are several ways in which soil can be
polluted with dumpsite, one of the ways can
materials are buried under the soil in a portion of
land that will be used for agricultural practices,
the dump will invariably turn out to be noxious
to any crop or plant that is around the vicinity.
economical practices, it should be properly treated.
After treatment the soil pollutant such as heavy
metal and BTEX, VOCs must be determined by
analytical methods. Percolation of contaminated
water into the soil is another way of polluting the
soil which many communities and societies are
not aware of it. Moreover, the contaminated water
(pollutant) into the soil measured by the different
analysis instruments. Also, solid waste seepage is
one of the common way of soil pollution, which
people neglect without knowing the implication
on the soil [28]. The most common chemicals
involved in causing soil pollution include solvents
from companies, pesticides from manufacturing
industries. As HSE role, the pollutants in soil of
near chemical industries controlled by chemistry
analyzers (AAS, UV-Vis and GC-FID). Soil
pollution is instigated by the presence of human-
made chemicals or other alteration in the natural
soil environment. It is characteristically set off
by agricultural chemicals, industrial activity, or
improper disposal of waste. The most common
chemicals engrossed are petroleum hydrocarbons,
polynuclear aromatic hydrocarbons which include
benzo (a) pyrene) and naphthalene, lead, pesticides,
and other toxic heavy metals. Contamination is
concurrent with the amount of industrialization and
concentration of chemical usage. The dread over
soil contamination stems principally from health
risks, from direct interaction with the contaminated
soil, depletes from the contaminants, and from
optional contamination of water sources within and
underlying the soil. Mapping of contaminated soil
areas and the resulting cleanup are tedious and costly
errands, requiring expansive measures of geology,
hydrology, and chemistry, computer modeling
skills, and GIS in Environmental Contamination,
alongside an energy about the historical backdrop
of industrial chemistry [29]. The effects of
dumpsite with regards to agricultural activities
include; reduced soil fertility, reduced nitrogen
of silt in tanks and reservoirs, reduced crop yield,
on the effects of dumpsite encourages the failure of
high crop yield and other activities carried out on
the soil. Many farmers complain of low yield and
the stunted growth of agricultural products without
prior knowledge of the effects of regular dumping of
garbage and other chemicals on dumpsites located
close to their agricultural farm lands [29]. The TLV
of heavy metal and VOCs in soil were reported by
FDA, EPA and WHO organizations. The levels of
heavy metals in the growing soil were highest for Fe,
Zn, Pb, and Cu. In the soil samples, the Fe content
The more content of heavy metals in soil caused
to toxic for human, foods and vegetables [29]. The
industrial activity such as chemical factory, paint
factory Oil Company caused to dispersed different
pollutions such as VOCs and heavy metals (Hg,
As, Ni, Co, V, Cd, Al, Mn) from their wastewaters
to soils. Chemical and allied industries comprise
of basic chemical manufacturing industries like
inorganic/organic chemicals, food industries, bulk
petrochemicals, pharmaceutical products and their
intermediates, polymers and their derivatives,
agricultural chemicals, acids, alkali, dyes, paper and
pulp, and fertilizers [30]. The chemical industries
pollution issues. Wastewater from chemical industry
contains mainly organic and inorganic pollutants.
These pollutants are toxic, mutagenic, carcinogenic,
and mostly nonbiodegradable. Complete treatment
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
88
chemical, and biological processes have been
considered for treatment of wastewater obtained
from chemical, biological, food, pharmaceutical,
pulp and paper, dye and textile industries. The choice
of methods for treatment of wastewater is based on
the type, nature, and concentration of contaminants.
reusable [30].
3.2. Analytical Method in Soil
For sample preparation of soil, the various analytical
procedure was used. As the VOCs analysis,
the soil directly analyzed by head space solid
phase extraction coupled to gas chromatography
spectrometer based on FID or mass detectors.
In addition, for heavy metals analysis, the soil
until constant weight was attained and then, the soil
3
HNO
3
minutes till brown fumes were produced. The
3
was
repeated over and over till white fumes appeared.
The solution was vaporized to about 5 on mantle
2
30% H
2
O
2
were added and the solution was placed
on the heating mantle to start the oxidation of
peroxide until effervescence subsided. Finally, the
heavy metals determined by the Atomic Absorption
Spectrophotometer (AAS, Perkin Elmer 2380) [24].
Due to Table 1, the Various analytical methods for
determination pollutants in soil and water samples.
3.3. Effect of Soil Pollutants on Human Health
There are different routes in which soil or land
pollution can affect human health either by short
term or long term exposure. When consumed some
of this harmful chemicals enters the digestive
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
Table 1. Various analytical methods for determination pollutants in soil and water samples
Sample Pollutant Instrument method Ref
Water VOCs GC-Ms SPE [3]
Soil
Water
Air
Toxic chemical
VOCs
Pesticides
Heavy metals
Phenols
GC-MS
F-AAS
HPLC
Nanotechnology over
conventional treatment
technologies
Adsorption
[2]
Water Trichloroethylene (TCE) GC-MS LLME–SPME [4]
Soil Heavy metals
F-AAS
ET-AAS
SCWEP [5]
Soil, Water, municipal
wastewater
Heavy metals CE-UV
DLLME
SDES
[6]
Water
Soil
Heavy metals AAS/SPME
Adsorption based on (CNMs),
(MNPs), (NIPs), (N-MOFs),
(SiNPs)
[9]
Soil and water
VOCs
Malondialdehyde Formaldehyde
HPLC-UV VALLME-HDES [16]
Water
Soil
Air
Aromatic hydrocarbons GC-MS
Pretreatment techniques
HS-SPME
[24]
Soil Hydrocarbon GC-MS SVE [25]
LLME–SPME: Liquid–liquid microextraction assisted solid phase microextraction, SCWEP: subcritical water extraction
nanomaterials,MNPs: magnetic nanoparticles ,NIPs: Nano-imprinted polymers , N-MOFs: Nano-based metal-organic frameworks,
SiNPs: Silica nanoparticles, SPME: Solid phase microextraction, VALLME-HDES: Vortex-assisted liquid-liquid microextraction
based on hydrophobic deep eutectic solvent, HS-SPME: Head space solid phase microextraction, SVE: Soil vapor extraction
89
Fig. 4. Mercury cell (production NaOH and Chlotine), dibenzodioxins (PCDD)
and polychlorinated dibenzofurans (PCDF) [32]
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
system, they are absorbed and taken to the liver,
these chemical will only be broken down by
the liver to certain extend in some cases these
chemicals which are not fully absorbed remains in
the guts which can be toxic on the gut lining. Direct
contact of contaminated soil to the skin can lead
to skin damage for example chromium which is a
soil pollutant, when this chemical is absorbed by
the skin it causes skin irritation [31]. Arsenic (AsIII
and AsV); which includes pesticides, coal burning
and wood preservative from preservative and agro
chemicals etc, which can be consumed through
ground water by absorbtion of the soil content
into the water. Intake of this over a long time
leads to GIT diseases, cardiovascular dysfunction
and liver damage. As Figure 4, Dioxin includes
the polychlorinated dibenzodioxins (PCDD) and
the polychlorinated dibenzofurans (PCDF) from
waste recycling industry and paper industry which
is consumed through contaminated foods such as
the immune system and also carcinogenic. Also,
cadmium (Cd
2+
) can be gotten from pigments,
sewage sludge, water pipes etc. it is mainly
consumed by animals but are harmless to animal
health, can affect human consuming animal
product and cause to MS and cancer. Fluoride as
water leads to joint stiffness and pains, it causes
leads to osteosclerosis. Mercury (Hg) consumed
by consumption of contaminated food (Sea Fish as
organic mercury C
2
H
5
-Hg and CH
3
-Hg) or metallic
mercury (mercury cell, vapor from petrochemical
industries) leads to damage of the central nervous
system(CNS), organ damage such as the liver and
kidney, it also causes teratology in a fetus and poor
brain development [32].
90
4. Water Pollutants, Analysis and Health
Effect
4.1. Water pollutants
Water contamination is an animated change in the
or hazardous as concerns food, agriculture,
recreation interest. The chemical hazards are the
Copper, Manganese, Lead, Cadmium, Phosphate,
Nitrate and so on, as the public health concern, the
ground water ought to be liberated from physical
and chemical hazards. Individuals in and around
the dumping site are relying on the ground water
for drinking and other homegrown purposes.
Other high-hazard bunch incorporates population
living near a waste dump and those, whose water
supply has gotten polluted either because of waste
danger of injury, and disease [33] Water is one of the
determinants of human earth framework. Diseases
may jump up through water contamination,
particularly groundwater tainting, and quickly
spread past human desire as a result of its stream
instrument. One of the main considerations that
make the earth tenable for humans is the presence
and animal cells, it is the premise of life and thusly
segment in the coordinated improvement of any
territory [33]. Most water pollution does not
continuously begin in the water itself. Practically
every human activity has a consequence on the
quality of the water environment. Dumpsites
that are seen in water ways and places that are
close to water bodies run off to the water bodies
during rainfall and assimilation to the soil which
causes of water pollution nevertheless, relatively
surprisingly sometimes include: Sewage from
household and from close industries that channel
their sewage directly or indirectly to the water
bodies, nutrients for agricultural farms that are
dumped close to water bodies are also an avenue
for water contamination and pollution, Heavy
metals, the xenobiotic compounds in wastewater,
avenue for water contamination. [34]. The amount
of debris in some waste sites as seen in Owerri in
groups (Table 2).
4.2. Analytical method in Water
For determination of heavy metals in water sample
HNO
3
aliquot of collected water sample. The solution was
processed on a routine basis to determine precision.
The concentrations of Cu, Zn, Fe, and Pb in the
determination VOCs any reagents have not added
to water samples. The metal concentration in the
water decreases in the following sequential order:
As > Pb > Zn > Cu = Al = Cr > Cd = Hg. Also, in
the sediment, the sequential order is as follows: Cr >
Zn > Cu > Pb > As > Cd > Hg [35]. For evaluation
of surface and groundwater on land and coastal sea
waters, we usually selected the heavy metals (Cd,
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
Table 2. The amount of debris in some waste sites as seen in Owerri in groups
Material Highly seen Moderately seen Not seen
Plastics
Rubber
Cloth
Glass/ceramics
Paper/cardboard
Metal
Wood
Other
91
Hg, Pb) as priority hazardous substances, and then,
the heavy metals (Cu, Zn, As, Cr) were chosen as
to a wide range of aquatic ecosystems [36]. Due to
the Hazardous Substances in Water, the chemical
and ecological status were determination with
environmental quality standards(EQS) for priority
(SP). According to EQS, the values of metals in
the surface waters for cadmium, mercury, copper,
chromium, zinc were obtained 0.04, 0.0025, 1.0,
1.2, zinc µg L-1, respectively [35]. Nsibande et al
quantum dot (CQDs) in water samples [37]. Cao et
al reported Metal–organic framework (MOF) for
extraction insecticides in water samples by dispersive
solid phase extraction (DSPE) [38]. Selahle and
Kachangoon used magnetic solid phase extraction
(MSPE) based on porphyrin organic polymer and
hydrophobic deep eutectic solvent(HDES) based
DLLME for determining of insecticide in water
[39, 40]. Bessonova and Ykowska reported the role
of ionic liquids for determination of pesticides and
VOCs in waters by DLLME [41, 42]. Also, the
determination pesticide, heavy metals and VOCs in
waters followed by DLLME –GC-MS and HPLC-
MS/MS [43,44]. Moreover, the analytical methods
for determination heavy metals and other pollutants
in waters followed by zeolitic imidazolate framework
(ZIF-7) based on MSPE and the biosensors in
waters [45-48]. Recently. The researchers used
SPE, MSPE, LLME, LLE, Liquid-phase membrane
extraction (LPME) for metal, pesticides, carboxylic
acids, phenol in water matrixes [49-52]. Also many
metals and VOCs were determined by different
ionic liquids and adsorbents (Table 3 and 4). Cloud
point extraction (CPE) has been utilized for the
preconcentration of cobalt, mercury and nickel, after
the arrangement of a complex with 1-(2-thiazolylazo)-
2-naphthol (TAN), and later examination by
octylphenoxypolyethoxyethanol (Triton X-114)
detection cycle were enhanced. Under the ideal
conditions, preconcentration of just 50 ml of sample
within the sight of 0.05% Triton X-114 permitted
the detection [53]. The current work depicts a
straightforward, dependable analytical strategy
in environmental water samples. The technique
depended on the cleanse of BTEX (a gathering
of unstable natural mixtures (VOCs)) from water
samples to a particular volume of acetonitrile
preceding making the analysis by superior liquid
array detector. The created method was upgraded
utilizing full factorial design, and the subsequent
ideal boundaries were applied in the examinations
recuperation was somewhere in the range of 94 and
106% with a maximum relative inclination of 5.9%,
relative standard deviation was under 7.7% (n = 10),
[53].
4.3. Effect of Water Pollutants on Human
Health
Since water have a wide range of usage all over
the world, the contaminated water makes gives ill
damages and causes serious health damage. Poor
or developing countries or communities are at risk
because their homes are often close to polluting
industries. Water borne pathogens are present in the
water due to fecal contamination and consumption
of untreated water. This lead to bacteria diseases,
pollutant, viral diseases and parasitic diseases
which was explain as below text.
Bacteria: such as typhoid which is caused by
Salmonella typhimurium bacteria, which mostly
infects the lining of the gastrointestinal tract
leading to constipation or diarrhea including high
fever it also affects organs such as the liver and
spleen. Cholera caused by vibrio cholerae , and
Dysentary caused by shigella, camphylobacter,
E. coli and salmonella bacteria species which
leads to intestinal infection causing dehydration,
excessive expulsion of water, blood and nutrient
through vomiting and excretion , this leads to body
weakness and stomach pains [75].
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
92
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
Table 3. Determination of heavy metal pollutants in water samples using ionic liquids or adsorbent
Ref.
Recovery
(%)
Heavy metal
interferences
Volume
(mL)
ILsAnalysis
preparation
method
SampleMetal
[54]97.8
Mn
2+
, Cd
2+
, Ni
2+
,
Zn
2+
5.0
[HMIM][BF
4
] and
NaPF
6
FAASISFME
Tap and lake
Water
Co
2+
[55]
More
than 95%
Cu
2+
, Zn
2+
, Cd
2+
20[HMIM][PF
6
]LC-MSLLME
Industrial
wastewater
As
3+
[56]100.3
Ni
2+
, Mn
2+
, Cu
2+
,
Zn
2+
, Cd
2+
, Fe
3+
,
Al
3+
, Rh
2+
,
10
[HMIM][PF
6
]
with [HMIM]
[Tf
2
]
F-AASDLLME
Mineral, tap,
and river water
Co
2+
[57]99.3
Fe
3+
, Zn
2+
, Pb
2+
,
Na
+
, K
+
, Ca
2+
and
15
[BMIM][PF
6
]
with PAN
F-AASDLLME
Lake and waste
water
Cd
2+
[58]99.5
Mn
2
, Zn
2+
, Cd
2+
,
Sn
2+
, Pb
2+
,
15Cyphos ILLC
IL-UADLLME-
SAP
River and lake
water
Cu
2+
[59]98.0
Pb
2+
, Cr
3+
, Al
3+
,
Sb
3+
, Cu
2+
, Cd
2+
,
10
[HMIM][Tf
2
N]
and PAN
UV-VisDLLME
Tap and mineral
water
Ni
2+
[60]98.4
Zn
2+
, Co
2+
, Cu
2+
,
Ni
2+
, Cd
2+
, Bi3+,
10
[BMIM][BF
4
] and
DPC
F-AASLLME
Mineral, sea,
and river water
Cr
3+
[61]98.3
Co
2+
, Ni
2+
, Zn
2+
,
and Cd
2+
10
[BMIM][PF
6
]
with Dithizone
F-AASUA-ILDME
Ground and
surface water
Pb
2+
[62]99.4Mn
2+
, Cu
2+
, Zn
2+
10
[BMIM][PF
6
] and
APDC
F-AAS
UA-MR- IL-
DLLME
river, and well
water
Cd
2+
[63]98.0
Ni
2+
, Mn
2+
, Cu
2+
,
Zn
2+
, Al
3+
, Hg
2+
20CNTs@DHSP
AT-
FAAS
WaterCd
2+
[64]96.0
Ni
2+
, Co
2+
, Cu
2+
,
Zn
2+
, Hg
2+
, Mn
2+
100
Dried activated
sludge (DAS)
F-AASSPEWaterSe
4+
[65]98.8%
Ag+, Cu
2+
Mg
2+
, Co
2+
Pb
2+
,
Zn
2+
25
(BDC)
2
(DABCO)
(MOF)
ET-AASWaterNi
2+
IL-HLLME: Ionic liquid for homogeneous liquid-liquid microextraction
LLME: Liquid-liquid microextraction
DLLME: Dispersive liquid-liquid microextraction
IL-UADLLME-SAP: Ionic liquid -
of the aqueous phase
UA-MR- IL-DLLME: Ultrasound-assisted magnetic retrieval-linked ionic liquid dispersive liquid–liquid microextraction
:
Pollutant: The diseases of air pollution include
the ischemic heart disease(IHD), the respiratory
infections(RI), the chronic obstructive pulmonary
disease (COPD), cancer. Heavy metals such as Hg,
V, Ni, Co and Pb created autoimmune diseases in
human. The autoimmune disease may indicate
organs. The most of autoimmune diseases is due to
extra concentration heavy metals in the environment
which is produced by industrial pollutants. Also,
the volatile organic compounds (VOCs) are entered
93
from environment to the human body and caused to
cancer. VOCs as hazardous chemicals can cause to
irritation, headaches, fatigue, nausea and dizziness
problems. High concentrations of VOCs cause
lungs cancer and damage the liver, kidney and CNS.
Viral: such as viral hepatitis A caused by hepatitis
A virus which infects the liver leading to jaundice
in some part of the body especially the sclera, loss
of appetite, fatigue and high fever. Poliomyelitis
caused by poliomyelitis virus leading to sore throat,
fever and paralysis of the limbs. Gastro enteric
diseases caused by rotavirus, adenovirus and other
viruses that are found in water contaminants.
Parasitic: which includes tapeworm intestinal
infestation, pinworms and round worms (Ascaris
lumbricoids) the eggs of this parasitic worms
are harmful to the human health, when their
eggs consumed through contaminated water or
ingested through contaminated food infects the
gastrointestinal system, digested eggs produces
live parasitic worms inside the body system, these
worms begin to compete for nutrient causing
abdominal pains and discomforts, retarded growth
and body weakness [76].
5. Air Pollutants, Analysis and Health
Effect
5.1. Air pollutants
Air contaminant or poison is a waste matter that
pollutes the air. Any material or chemical waste
product, which adjudicates the air and other natural
reserves harmful or generally impracticable. There
are several factor that promote the severity of air
pollution, they include its persistence, chemical
nature and the concentration. Solid waste makes
a few noxious gases, for example, Hg
o
, VOCs,
Table 4. Determination of VOCs pollutants in water samples using ionic liquids or adsorbent
Ref.
Recovery
(%)
LOD(μg/L)
Volume
(mL)
ILsAnalysis
preparation
method
SampleVOCs
[66]98.25----------
Sulfolane IL
GC-FID LTTMsPTIBenzene
[67]96.30.355.0
[BMIM][PF
6
]
and [HMIM]
[PF
6
]
HPLCDLLME
Rain
water
DDD
[68]105.10.045160
BMIM][BF
4
]
and [NH
4
][PF
6
]
HPLC
DLLME
River
water
Estradiol
benzoate (EB)
[69]99.9-----10
[BMIM][Tf
2
N]
[HMIM][Tf
2
N]
Color
reaction
LEWaterPhenol
[70]98.9-99.4
3.0×10
10
Carbon
Nanoadsorbent
VoltammetryCPBDDEWaterBTEX
[71]95.4-102%
0.023
-----NanostructureGC
Solvent
extraction
Water
Ethanol,
Heptane
[72]95%-------15MOF/ zeolitesGC
Solid liquid
separation
Water
Xylene
[73]
96.8-102------------CNTs@PhSA
SHS-GC-
MS
WaterBenzene
[74]98.7%--------------
CuONPsHS-GCSPEWater
Benzene
Toluene
CPBDDE: Cathodically pretreated boron‐doped diamond electrode
LTTMs: Low transition temperature mixtures
PTI: Petrochemical industry
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
94
BTEX, H
2
S, suspended Sulfur Dioxide (SO
2
),
oxides of Nitrogen (NO
X
), Carbon Monoxide
(CO), Respirable Suspended Particulate Matter
(RSPM) and Suspended Particulate Matter (SPM).
The residue delivered from different sources can
create a gathering of sicknesses going from a
straightforward cold to hazardous illnesses like
cancer [77].
5.2. Analytical Methods in Air
Benzene, Toluene, Ethylbenzene and Xylenes
isomers (BTEX) are a group of highly volatile
gaseous pollutants frequently found in indoor and
outdoor air. It is known from the literature that
these compounds have a negative impact on the
environment since they contribute to the formation
of ozone and other photochemical oxidants.
Moreover, BTEX are either known for being, or
suspected to be, irritants, neurotoxins, allergens
or carcinogens and their exposure on a long term
basis presents a serious threat to the human health.
Therefore, implementing effective strategies for
pollution control is of paramount importance to
limit human exposure and prevent the environment
degradation [78]. These days, various techniques
dependent on physicochemical or biological
cycles have been produced for gaseous pollutant’s
expulsion like thermal, plasma, synergist or
photocatalytic oxidation, condensation, membrane
division, biological degradation, absorption
and adsorption. Notwithstanding, the pollutant
generally low, running from sub ppb level to 100
not all evacuation techniques can be successful
at such low focus ranges. Moreover, a portion
of these methods are costly or require normal
upkeep restricting their utilization at homegrown
scale. Among them, adsorption has been shown
to be a method that displays a decent trade off
[78]. Since BTEX focuses are
typically exceptionally low, the combination of
preconcentration gadgets is for the most part
expected to expand the affectability of these
methods. Along these lines, in the referenced
pollutant particles and concentrate the example
that is destined to be, thusly, dissected by ordinary
gas chromatography. The adsorbent prerequisites
in pollutant evacuation just as gas investigation
incorporate a negligible leap forward, huge
adsorption limit, thermal solidness and selectivity
to the designated pollutants. Furthermore, the
desorption temperature ought to be moderate to
empower a powerful, modest and quick adsorbent
recovery [79]. Carbon monoxide (CO) has a
characteristic infrared absorption near 4.6nm.
The absorption of infrared radiation by the carbon
monoxide molecule can therefore be used to
measure the concentration of carbon monoxide in
the presence of other gases. The Non-dispersive
infrared photometry method [NDIR] is based on
this principle. Most commercially available NDIR
interferences from other gases. They operate at
atmospheric pressure, and the most sensitive
analyzers are able to detect minimum carbon
monoxide concentrations of about 0.05 mg m
-3
(0.044 ppm). Interferences from carbon dioxide
and water vapour can be dealt with so as not to
affect the data quality. Also, the another sensitive
method for measuring low background levels of
carbon monoxide (CO) is gas chromatography
This technique is an automated, semi-continuous
method in which carbon monoxide is separated
from water, carbon dioxide and hydrocarbons
other than methane by a stripper column. Carbon
monoxide and methane are then separated on
an analytical column, and the carbon monoxide
is passed through a catalytic reduction tube,
where it is converted to methane. The carbon
monoxide (converted to methane) passes through
signal is proportional to the concentration of
carbon monoxide in the air. This method has
been used throughout the world. It has no known
interferences and can be used to measure levels
from 0.03 to 50 mgm
-3
(0.026 to 43.7 ppm).
Nitrogen oxides are one of the primary pollutants
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
95
just as the evaluation standards of the air quality.
Nitrogen oxides (NO) in the atmosphere adversely
affect people principally through the respiratory
system, which might cause intense and constant
health issues. In this manner, the investigation of
examination and detection methods for nitrogen
oxides will be critical. There are numerous
methods for the determination of nitrogen oxides
like ion chromatography, chemiluminescence,
has attracted a lot of consideration and been applied
generally for the location of nitrite for the high
sensitivity, selectivity, low limit of recognition and
straightforward activity. As per the writing, NO
2
natural colors and NO
2
3
the fundamental frameworks for the assurance of
for deciding degrees of sulfur dioxide (SO
2
) in
the air incorporate ion chromatography, titration,
calorimetry, mass spectrometry, conductimetry,
detection, and turbidimetry. Ion chromatography is
by all accounts the most sensitive of these methods
sulfur dioxide. Sulfur dioxide has additionally been
estimated in stack gases. Methods for estimating
sulfur dioxide in stack gases incorporate beat
isn’t found in water since it is decreased to sulfuric
corrosive in water. Colorimetry, titration, and either
corrosive distillation (AD) or soluble base extraction
(AE) ion exclusion chromatography (IEC) with
electrochemical detection (ED) can be utilized to
gauge sulfur dioxide in food and beer. The analytical
methods in air was shown in (Table 5.)
5.3. Ways of Air pollution
Dumpsite emit poisonous gases which enter
the air and become detrimental to man and the
particulate matter, which include black carbon
or dust, popularly refers to as smut, which is a
short-term climate pollutant with global warming
happens when biodegradable waste decomposes
with air. Chemical factories, oil company,
petrochemical Company and industrial chemical
activities caused to relapsed VOCs, BTEX, the
metallic and inorganic mercury, H
2
S in air [79].
5.4. Effect of Air Pollution on Human Health
Air pollution is determined by presence of
particles in the air which are known as pollutants
and are presents in large quantities for long
periods of time. Such pollutants include particles
hydrocarbons, carbon monoxide, carbon(IV)
oxide, lead nitrogen oxide(NO) and sulfur oxide.
This pollutant when inhaled into the body system
either due to long term or short term effect causes
serious health implications such as respiratory
disorders, cardiovascular dysfunction, neurogenic
instability such as and pathological diseases [80].
Carbon Monoxide: When there is exposure to
this gas it leads to tiredness, dizziness, headaches,
nausea, confusion, and impaired vision. Long
term exposures can lead to brain damage, heart
weakness. When inhaled it combines with
Table 5. The analytical methods in air
Air pollutant Type Ref
S0
2
Cu–Ce catalysts supported on activated carbon [2,88]
Dust, H
2
S Fluorinated MOF [83-85]
0
3
, Oxidant Adsorbent [20, 79]
Hydrocarbons Metamodel to a spatially-distributed housing stock [79]
NO, NO
2
2D Hybrid Nanomaterials [82,78]
CO Gas sensors [81]
CO
2
Gas sensors [81]
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
96
hemoglobin in the blood by displacing oxygen
and forming carboxyhemoglobin which causes
the cell and organs to become hypoxic (lacking
of oxygen). The brain and heart consumes large
amount of oxygen but due to the toxicity of
carbon monoxide the brain and heart cells will
lack adequate oxygen for proper functioning
[81].
Nitrogen Oxide: Nitrogen oxide are pollutants
that mainly affects the respiratory system and
causing respiratory metaplasia, short term
exposure to this can increase a person chance
of respiratory infections and asthma. Long term
exposures can lead to chronic lung diseases.
When inhales the respiratory airways response
effectively leading to allergic reaction causing
increase in airway neutrophilia and bronchial
hyper responsiveness, it reduces the antioxidant
effects of tissues, it replaces type I alveolar
epithelial cells and ciliated epithelial cells with
more oxidant resistant type II and non- ciliated
cara cells [82].
Sulfur Dioxide: High concentrations of sulfur
dioxide causes skin irritation, irritation of mucus
membranes of the eyes, nose, lungs etc. it reduces
the function of the lungs it makes breathing
are sensitive to this [83]. Also, the exposure of
NO
2
and SO
2
cause to many diseases such as the
respiratory system, skin irritation and irritation
of mucus [83-85].
6. Urban Effects for Pollutants
Urban effects of dumpsite have been monitored
in developed cities while in some area, the effects
of this dumpsite are still overlooked which in
turn leads to clogging of drains, Inundation
of areas, public health problems, pollution of
drinking water sources, foul smell and release of
gases, ecological imbalance, release of pollutant
gases, release of radioactive rays causing health
problems, increased salinity, reduced vegetation
and other effects. Pollution runs off into rivers
life, crops and grain developed on dirtied soil
may give the contaminations to the customers,
contaminated soil may presently don’t develop
crops and grub, soil structure is harmed (clay
ionic structure impaired), consumption of
establishments and pipelines, debilitates soil
solidness, may deliver fumes and hydrocarbon
into structures and basements, may make
poisonous tidies, may poison children playing in
the region [86].
7. Remediation of Pollution
7.1. Incineration
Incineration is a waste treatment measure that
includes the burning of organic substances
encased in waste materials. Incineration and other
high-temperature waste treatment frameworks are
depicted as “thermal treatment”. Incineration of
waste materials changes over the waste into ash,
flue gas, and heat. The ash is generally formed by
the inorganic constituents of the waste, and may
appear as strong bumps or particulates conveyed
by the flue gas. The flue gases must be destroyed
of gaseous and particulate contaminations before
they are scattered into the environment. In certain
conditions, the heat created by incineration can
be utilized to deliver electric force. Incineration
with energy repossession is one of a few waste-
to-energy (WtE) advances such as pyrolysis,
anaerobic digestion and gasification [87]. In
certain nations, incinerators manufactured only
a couple many years prior frequently did exclude
a materials detachment to eliminate dangerous,
cumbersome or recyclable materials before
burning. This implies that while incineration
doesn’t totally supplant landfilling, it altogether
diminishes the vital volume for removal.
Dump trucks frequently diminish the volume
of waste in an underlying compressor before
conveyance to the incinerator. Then again,
at landfills, the volume of the uncompressed
trash bin be decreased by around 70% by
utilizing a stationary steel compressor, yet
with a huge energy cost. In numerous nations,
more straightforward waste compaction is a
typical practice for compaction at landfills.
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
97
Incineration has especially solid advantages for
the treatment of certain waste sorts in specialty
areas such as clinical wastes and certain perilous
wastes where microbes and poisons can be
devastated by high temperatures. Denmark and
Sweden have been pioneers in utilizing the
energy created from incineration for more than
a century, in restricted joined heat and force
offices supporting region heating plans [88].
7.2. Recycling
Recycling is viewed as a helpful recuperation
practice which alludes to the assembly and reuse
of waste materials which incorporate beverage
holders, water compartment and so forth. The
materials from which the things are made can
be measure again into new items. Material for
recycling may be gathered autonomously from
general waste utilizing assortment vehicles
networks, the maker of the waste is required
to isolate the materials into various receptacles
which may be paper canister, plastics container,
metals container and so on, prior to its assortment
[89]. While I a few spots and networks, every
recyclable substance and materials are unloaded
in a solitary assortment canister and are sorted
customer items reused comprise of steel from
food and aerosol cans, copper such as wire, old
steel furnishings or equipment, aluminum such
as beverage cans, polyethylene and PET bottles,
newspapers, glass bottles and jars, paperboard
cartons, light paper and magazines and corrugated
and complex materials such as computers and
electronic equipment is more testing, because of
the additional destroying and division required
[90]. The category of material acknowledged
for recycling varies by city and nation. Every
city and nation has different recycling programs
set up that can deal with the countless sorts of
recyclable materials. In any case, exact variety in
gathering is reproduced in the resale estimation
of the material whenever it is reprocessed [91].
7.3. Resource recovery
Resource recovery is the methodical digression
of waste, which was envisioned for disposal,
for a precise next use. It is the handling of
recyclables to achieve or recover materials and
resources, or transform to energy. These actions
are accomplished at a resource retrieval facility
where the machines or equipment for recovery are
readily available. Resource retrieval mechanism
is not only environmentally imperative, but it
is correspondingly cost effective. It reduces the
amount of waste products for disposal, it also
natural resources. This method of waste
management can be used in developing countries
in order to generate and maintain their economy.
As an example of how resource recycling can
contain precious metals which can be recycled to
boards [91].
7.4. Avoidance and reduction methods
This method includes finding possible ways
to minimize the generation of waste which
will eventually be dumped at the dumpsites.
The reduction on the use of plastic, rubber,
nylon and polythene will go a long way in
waste reduction. An imperative method of
waste dump management is the preclusion of
waste material being fashioned, also known
as waste reduction [53]. Approaches that can
be followed to avoid these waste include the
reuse of second-hand materials and products,
fixing and maintaining of broken items instead
of purchasing new ones, trying to produce
material sand products that re reusable or
refillable for instance cotton instead of plastic
shopping bags), aiding consumers to always
use products that are reusable and not always
disposable such as cutlery etc [92].
7.5. Bioremediation Technology
The bioremediation is seen as the usage of living
microorganisms to lower the environmental
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
98
pollutants and chemicals into less contaminated
and poisonous forms (Fig.5). It makes use of
naturally stirring bacteria, fungi or plants to
decontaminate substances hazardous to human
health and the environment in general. It is
also seen as the use of biological systems to
reduce the concentrations of crude oil wastes
from contaminated soil [93]. Bioremediation
approach can be as unpretentious as applying a
garden fertilizer to an oil-contaminated soil, or
as multifaceted as an engineered treatment “cell”
where soils or other media are manipulated,
aerated, heated, or treated with various chemical
compounds to promote degradation [93].
7.6. Chemical adsorption Process
An adsorbent is an insoluble material covered
by liquid on the surface, including vessels and
pores. A material is supposed to be adsorbent
when it has the ability to contain an unmistakable
measure of liquid in little chambers like a wipe.
Adsorbents assume an indispensable part in
chemical absorption, which happens when a
surface. Adsorbents that are equipped for
adsorbing carbon dioxide incorporate carbon
materials (like initiated carbon and carbon
(like 5A and 13), mesoporous silicas (like SBA
and MCM), metal-natural frameworks, metal
oxides (like calcium oxide and magnesia),
particle trade resins, and layered twofold
hydroxides, (for example, hydrotalcites). Be that
as it may, the adsorbents including physisorption
show immaterial adsorption limit with respect
to carbon dioxide at high temperatures. The
adsorption limit and selectivity are determinants
of adsorbent separating the CCS measures
[94]. Graphene is a carbon-based nanomaterial
with a two-dimensional design, high explicit
surface region and great substance strength. It is
accessible in different structures, for example,
perfect graphene, graphene oxide and decreased
graphene oxide. Graphene might be oxidized
to add hydrophilic gatherings for heavy metal
expulsion. adsorbed chromium onto the outer
layer of graphene oxide and the most extreme
adsorption limit found was around 92.65 mg/g at
an ideal pH of 5. This adsorption of chromium on
graphene oxide was observed to be endothermic
and unconstrained [95]. The graphene, MWCNTs
and nanoparticles of metals such as AgNPs were
used for adsorption pollutants from air and water
samples by chemical or physical adsorption of
adsorbents with high surface area. Ashori et al
showed that a novel nanosorbent based on IL@
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
Fig. 5. Bioremediation Technology [92]
99
MWCNTs for benzene removal from air (Fig.
6a and 6b). Osanloo et al used the AgNPs for
removal mercury from air [96]. Shirkhanloo et al
used the silver nanoparticles on glassy balls for
removal mercury vapor from air [96]. Khaligh
et al reported the carboxyl-functionalized
nanoporous graphene (NG-COOH) as adsorbent
for extraction and speciation of inorganic and
organic mercury (Hg (II) and R-Hg ; CH
3
Hg
+
/
C
2
H
5
Hg
+
procedure [97]. Mousavi et al showed an amine-
functionalized mesoporous silica UVM-7 can be
extracted the manganese (II, VII) ions from water
was determination by the AT-FAAS [98]. Rashidi
et al used the hybrid nanoadsorbent which was
prepared by depositing graphene on the zeolite
clinoptilolite by chemical vapor deposition for
adsorption of lead(II) and cadmium(II) in water
samples by the USA-DMSPE procedure [99].
Rakhatshah et al reported the styrene adsorption
liquid (TSIL) immobilized on multi-walled
carbon nanotubes (MWCNTs@[Hemim][BF
4
])
which was determined by USA-DCC-µ-SPE
procedure coupled to GC-FID. The styrene
affected on human body and caused cancer,
problem in CNS and liver [100].
Fig.6b. [101]
Fig.6a. [101]
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
100
8. Conclusions
Pollution caused by chemical industries and
dumpsite is the most prevalent problem in the
environment especially when it comes to soil
pollution caused by manmade pollution. The release
of waste materials into the environment is receiving
worldwide attention. The effect of dumpsite
pollution on soil properties was investigated by
reviewing studies done in Owerri in Nigeria. The
various analytical methods were used for water,
soil and air analysis. The pollutant can be removed
from environment by different techniques such
as Bioremediation, Biodegradation, adsorption,
oxidation and reduction.
9. Acknowledgements
The authors wish to thank the Chemistry Department,
Imo State University Owerri, Imo State Nigeria;
Chemistry Department, Chukwuemeka odimegwu
Ojukwu University Uli, Anambra Nigeria and
Medicine Department, Gregory University, Uturu
Abia State, Nigeria.
10. References
[1] K. T. Semple, B. J. Reid, T. R. Fermor, Impact
of composting strategies on the treatment of
soils contaminated with organic pollutants,
Environ. Pollut., 112 (2011) 269-283.
[2] R.K. Ibrahim, M. Hayyan, M.A. Al-saadi,
A. Hayyan, S. Ibrahim, Environmental
application of nanotechnology; air, soil,
and water, Environ. Sci. Pollut., 23 (2016)
13754–13788.
[3] A. Andrade-Eiroa, M. Canle, V. Leroy-
Cancellieri, V. Cerdà, Solid-phase extraction
of organic compounds: A critical review (Part
I), TrAC- Trends Anal. Chem., 80 (2016)
641–654.
[4] M. Zhang, P. de B. Harrington, Determination
of Trichloroethylene in Water by Liquid–
Liquid Microextraction Assisted Solid Phase
Microextraction, Chromatogr., 2 (2015) 66-
78.
[5] M.N. Islam, H.Y. Jung, J.H. Park, Subcritical
water treatment of explosive and heavy
metals co-contaminated soil: Removal of
the explosive, and immobilization and risk
assessment of heavy metals, J. Environ.
Manag., 163 (2015) 262–269.
[6] M.H. Habibollahi, K. Karimyan, H. Arfaeinia,
N. Mirzaei, Y. Safari, R. Akramipour,
determination of heavy metals in soil and
vegetables irrigated with treated municipal
wastewater using new mode of dispersive
liquid–liquid microextraction based on the
GF-AAS, J. Sci. Food Agric., 99 (2019) 656–
665.
[7] F. Gianì, R. Masto, M.A. Trovato, P.
Malandrino, M. Russo, G. Pellegriti, P.
Vigneri, R. Vigneri, Heavy metals in the
environment and thyroid cancer, Cancers, 13
(2021) 4052.
[8] S. Dugheri, A review of micro-solid-phase
extraction techniques and devices applied
in sample pretreatment coupled with
chromatographic analysis, Acta Chromatogr.,
12 (2020) 35.
[9] W. A. Khan, Nanomaterials-based solid phase
extraction and solid phase microextraction
for heavy metals food toxicity, Food Chem.
Toxicol., 145 (2020)111704.
[10] W. Setyaningsih, T. Majchrzak, T. Dymerski,
J. Namie´snik, M. Palma, Key-Marker
volatile compounds in aromatic rice (Oryza
sativa) Grains: An HS-SPME extraction
method combined with GC × GC-TOFMS,
Molecules, 24 (2019) 4180.
[11] NR. Biata, KM. Dimpe, J. Ramontja, N. Mketo,
PN. Nomngongo, Determination of thallium
in water samples using inductively coupled
plasma optical emission spectrometry (ICP-
OES) after ultrasonic assisted-dispersive
solid phase microextraction, Microchem. J.,
137 (2018) 214-22.
[12] SZ. Mohammadi, A. Sheibani, F. Abdollahi,
Speciation of Tl(III) and Tl(I) in hair samples
by dispersive liquid–liquid microextraction
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
101
spectrometry determination, Arab. J. Chem.,
9 (2016) S1510-S5.
[13] O. B. Ifeoluwa, Harmful effects and
management of indiscriminate solid waste
disposal on human and its environment in
Nigeria: A Review, Glob. J. Res. Rev., 6
(2019) 1-7.
[14] S. C. Ihenetu, F. C. Ihenetu, G. I. Kalu,
Determination of heavy metals and
physicochemical parameters of crude oil
polluted soil from Ohaji Egbema Local
Government in Imo State, Open J. Yangtze
Gas Oil, 2 (2017) 161-167.
[15] S. Zhu, J. Zhou, H. Jia, H. Zhang, Liquid–
liquid microextraction of synthetic pigments in
beverages using a hydrophobic deep eutectic
solvent, Food Chem., 243 (2018) 351–356.
[16] A. Safavi, R Ahmadi, A. M. Ramezani,
Vortex-assisted liquid-liquid microextraction
based on hydrophobic deep eutectic solvent
for determination of malondialdehyde and
formaldehyde by HPLC-UV approach,
Microchem. J., 143 (2018) 166–174.
[17] S. McMichael, P. Fernández-Ibáñez, J. Byrne,
A review of photoelectrocatalytic reactors for
water and wastewater treatment, Water, 13
(2021) 1198.
[18] D. Alrousan, A. Afkhami, K. Bani-Melhem,
P. Dunlop, Organic degradation potential of
real greywater using TiO
2
based advanced
oxidation processes, Water, 12 (2020) 2811.
[19] R. Ahmadi, G. Kazemi, A. M. Ramezani,
A. Safavi, Shaker-assisted liquid-liquid
microextraction of methylene blue using deep
eutectic solvent followed by back-extraction
and spectrophotometric determination,
Microchem. J., 145 (2019) 501–507.
[20] K. Maheep, P. Vijay, Review on solid waste:
Its Impact on air and water quality, J. Pollut.
Control, 8 (2020) 242-252.
[21] L. O. Odokumaand, A. A. Dickson,
rain-forest soil, Global J. Environ. Sci., 2
(2003) 29–40.
[22] A. M. Ramsay, P. J. Warren, A. T. Duke,
R. Hill, Effect of bioremediation on the
microbial community in oiled mangrove
sediments, Marine Pollut. Bull., 41 (2000)
413-419.
[23] J. Sabate, M. Vinas, A. M. Solanas,
Laboratory-scale bioremediation experiments
on hydrocarbon-contamined soil, J. Int.
Biodeter. Biodegr. J., 54 (2014) 19-25.
[24] N. Raza, B. Hashemi, K.H. Kim, S.H. Lee, A.
Deep, Aromatic hydrocarbons in air, water, and
soil: sampling and pretreatment techniques,
TrAC- Trends Anal. Chem., 103 (2018) 56–73.
[25] C. Labianca, Remediation of a petroleum
hydrocarbon-contaminated site by soil vapor
extraction: A full-scale case study, Appl.
Sci., 10 (2020) 4261.
earthworms and organic additives on the
biodegradation of oil contaminated soil,
Appl. Soil Ecol., 36 (2007) 53-62.
[27] K. Van Gestel, J. Mergaert, J. Swings,
Coosemans, J. Ryckebore, Bioremediation of
diesel oil-contaminated soil by composting
with biowaste, Environ. Pollut., 5 (2001)
361-368.
[28] N. Vasudevan, P. Rajaram, Bioremediation of
oil sludge- contaminated soil, Environ. Int.,
26 (2001) 409-411.
[29] D. Hou, D. O’Connor, A. D. Igalavithana,
Metal contamination and bioremediation
of agricultural soils for food safety and
sustainability, Nat. Rev. Earth Environ., 1
(2020) 366–381.
[30] G. Qin, Soil heavy metal pollution and
food safety in China: Effects, sources
and removing technology, Chemosphere,
267 (2021)129205.
[31] M. Walter, K.S.H. Boyd-Wilson, D.
McNaughton, G. Northcott, Laboratory
trials on the bioremediation of aged
pentachlorophenol residues, J. Int. Biodeter.
Biodegr., 3 (2005) 121-130.
[32] B. A. Wrenn, A. D. Venosa, Health effects of
pollution, Can. J. Microbiol., 42 (1996) 252–258.
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
102
[33] K. Yones, F. Kiani, L. Ebrahmi, The effect
of land use change on soil and water quality
in northern Iran, J. Mountain Sci., 9 (2012)
798–816.
[34] P. Roccaro, M. Sgroi, F. G. Vagliasindi,
Removal of xenobiotic compounds from
wastewater for environment protection:
Treatment processes and costs, Chem. Eng.
Trans., 3 (2013) 32-50.
[35] Regulation for determining the status of
surface waters; ministry of agriculture and
rural development, Ministry of health and
the ministry of sustainable development and
tourism: Podgorica, Montenegro, 1–39, 2019.
[36] Government of the republic of Montenegro:
of surface and ground water, 2021. https://
www.morskodobro.com/dokumenti/uredba_
voda.pdf.
[37] S. A. Nsibande, P. Forbes, Fluorescence
detection of pesticides using quantum dot
materials e a review, Anal. Chim. Acta, 945
(2016) 9–22.
[38] X. Cao, Z. Jiang, S. Wang, S. Hong, H. Li,
C. Zhang, Metal–organic framework UiO-66
for rapid dispersive solid phase extraction of
neonicotinoid insecticides in water samples,
J. Chromatogr. B, 4 (2018) 1077–1078.
[39] S. K. Selahle, N. J. Waleng, A. Mpupa,
P. N. Nomngongo, Magnetic solid phase
extraction based on nanostructured magnetic
porous porphyrin organic polymer for
simultaneous extraction and preconcentration
of neonicotinoid insecticides from surface
water, Front. Chem., 6 (2020) 8-22.
[40] R. Kachangoon, J. Vichapong, Y.
Santaladchaiyakit, R. Burakham, S.
Srijaranai, An eco-friendly hydrophobic deep
eutectic solvent-based dispersive liquid–
liquid microextraction for the determination
of neonicotinoid insecticide residues in
water, soil and egg yolk samples, Molecules,
12 (2020) 27-85.
[41] E. A. Bessonova, V. A. Deev, L. A. Kartsova,
Dispersive liquid–liquid microextraction of
pesticides using ionic liquids as extractants,
J. Anal. Chem., 8 (2020) 99-129
Modern approaches in dispersive liquid–
liquid microextraction (DLLME) based on
ionic liquids: A review, J. Mol. Liq., 2 (2018)
319–393.
[43] A. Szarka, D. Turková, S. Hrouzková,
Dispersive liquid–liquid microextraction
followed by gas chromatography–mass
spectrometry for the determination of
pesticide residues in nutraceutical drops, J.
Chromatogr. A, 3 (2018) 126–134.
[44] I. Timofeeva, A. Shishov, D. Kanashina,
D. Dzema, A. Bulatov, on-line in-syringe
sugaring-out liquid–liquid extraction coupled
with HPLC-MS/MS for the determination of
pesticides in fruit and berry juices, Talanta, 3
(2017) 76-117
[45] M. Nasiri, H. Ahmadzadeh, A. Amiri, Sample
preparation and extraction methods for
pesticides in aquatic environments: A review,
172.
[46] E. A. Songa, J. O. Okonkwo, Recent
approaches to improving selectivity and
sensitivity of enzyme-based biosensors for
organophosphorus pesticides: a review,
Talanta, 5 (2016) 289–304.
techniques for trace element determination,
Phys. Sci. Rev., 2 (2017) 1–14.
[48] S. Zhang, W. Yao, J. Ying, H. Zhao,
Polydopamine-reinforced magnetization of
zeolitic imidazolate framework ZIF-7 for
magnetic solid-phase extraction of polycyclic
aromatic hydrocarbons from the air-water
environment, J. Chromatogr. A, 4 (2016) 18–
26.
[49] L. Prakel, B. Schuur, Solvent developments
for liquid–liquid extraction of carboxylic
acids in perspective, Sep. Purif. Technol., 9
(2019) 35–57.
[50] N. N. Hidayah, S. Z. Abidin, The evolution of
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
103
mineral processing in extraction of rare earth
elements using solid–liquid extraction over
liquid–liquid extraction: a review, Min. Eng.,
3 (2017) 103–113.
[51] J. M. Kokosa, Selecting an extraction solvent
for a greener liquid phase microextraction
(LPME) mode-based analytical method,
247.
of targeted pesticides from manufacturing
feed-stream recycle, Environ. Technol., 3
(2017) 78–84.
[53] C. Zheng, L. Zhao, X. Zhou, Z. Fu, A.
Li, Treatment technologies for organic
wastewater, Water Treat., 11 (2013) 250–286.
[54] M. Hosseini, N. Dalali, S. Moghaddasifar,
Ionic liquid for homogeneous liquid-liquid
microextraction separation/preconcentration
and determination of cobalt in saline
samples, J. Anal. Chem., 69 (2014) 1141–
1146.
[55] L. Fischer, T. Falta, G. Koellensperger, Ionic
liquids for extraction of metals and metal
containing compounds from communal and
industrial waste water, Water Res., 45 (2011)
4601–4614.
[56] M. Mirzaei, N. Amirtaimoury, Temperature-
induced aggregation ionic liquid dispersive
liquid-liquid microextraction method for
separation trace amount of cobalt ion, J.
Anal. Chem., 69 (2014) 503–508.
[57] S. Khan, M. Soylak, T. G. Kazi, Room
temperature ionic liquid-based dispersive
liquid phase microextraction for the
separation/preconcentration of trace Cd
2+
as
1-(2-pyridylazo)-2-naphthol (PAN) complex
from environmental and biological samples
and determined by FAAS, Biol. Trace Elem.
Res., 156 (2013) 49–55.
[58] J. Werner, Ionic liquid ultrasound-assisted
dispersive liquid-liquid microextraction
for preconcentration of heavy metals ions
prior to determination by LC-UV, Talanta,
182 (2018) 69–73.
[59] R. Khani, F. Shemirani, Simultaneous
determination of trace amounts of cobalt
and nickel in water and food samples using
a combination of partial least squares method
and dispersive liquid–liquid microextraction
based on ionic liquid, Food Anal. Methods, 6
(2013) 386–394.
[60] B. Majidi, F. Shemirani, Salt-assisted liquid-
liquid microextraction of Cr(VI) ion using
an ionic liquid for preconcentration prior to
spectrometry, Microchim. Acta, 176 (2012)
143–151.
[61] S. Nizamani, T. G. Kazi, H. I. Afridi,
Ultrasonic-energy enhance the ionic liquid-
based dual microextraction to preconcentrate
the lead in ground and stored rain water
samples as compared to conventional shaking
method, Ultrasonics Sonochem., 40 (2018)
265–270.
[62] L. Yao, X. Wang, H. Liu, Optimization
of ultrasound-assisted magnetic retrieval-
linked ionic liquid dispersive liquid–liquid
microextraction for the determination
of cadmium and lead in water samples
by graphite furnace atomic absorption
spectrometry, J. Ind. Eng. Chem., 56 (2017)
321–326.
[63] J. Rakhtshah, Separation and determination
of cadmium in water samples based on
functionalized carbon nanotube by syringe
extraction, Anal. Methods Environ. Chem. J.,
4 (2021) 5-15.
[64] M. Ghazizadeh, Speciation and removal of
selenium (IV, VI) from water and wastewaters
based on dried activated sludge before
determination
spectrometry, Anal. Methods Environ. Chem.
J., 4 (2021) 36-45.
[65] N. Motakef Kazemi, Zinc based metal–
organic framework for nickel adsorption in
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
104
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
water and wastewater samples by ultrasound
assisted-dispersive-micro solid phase
extraction coupled to electrothermal atomic
absorption spectrometry, Anal. Methods
Environ. Chem. J., 3 (2020) 5-16.
[66] S. Ma, J. Li, L. Li, X. Shang, S. Liu, C.
Xue, Liquid–liquid extraction of benzene
and cyclohexane using sulfolane-based low
transition temperature mixtures as solvents,
experiments and simulation, Energy Fuels, 32
(2018) 8006–8015.
[67] X. Wang, Q. C. Xu, C. G. Cheng, R. S.
Zhao, Rapid determination of DDT and its
metabolites in environmental water samples
with mixed ionic liquids dispersive liquid–
liquid microextraction prior to HPLC-
UV, Chromatographia, 75 (2012) 1081–1085.
[68] R. Zhang, X. Cheng, J. Guo, H. Zhang, X.
Hao, Comparison of two ionic liquid-based
pretreatment methods for three steroids’
separation and determination in water
samples by HPLC, Chromatographia, 80
(2017) 237–246.
imide based ionic liquids to extract phenolic
compounds, J. Chem. Thermodynamics, 131
(2019) 159–167.
[70] G. Garcia de Freitas Junior, TM. Florêncio, RJ.
Mendonça, GR. Salazar‐Banda, Rt. Oliveira,
Simultaneous voltammetric determination of
benzene, toluene and xylenes (BTX) in water
using a cathodically, pre-treated boron-doped
diamond electrode, Electroanal., 31(2019)
554-559.
[71] X. Li, Z. Jia, J. Wang, H. Sui, L. He, OA.
Volodin, Detection of residual solvent in
solvent extracted unconventional oil ore
gangues, J. Eng. Thermophys., 28 (2019)
499-506.
[72] N. Sun, SQ. Wang, R. Zou, WG. Cui, A
Zhang, T. Zhang, Q. Li, ZZ. Zhuang, YH.
Zhang, J. Xu, MJ. Zaworotko, Benchmark
selectivity p-xylene separation by a non-
porous molecular solid through liquid or
vapor extraction, Chem. Sci., 10 (2019)
8850-8854.
[73] S. Teimooria, A. H. Hassanib, M. Panaahie,
Extraction and determination of benzene
from waters and wastewater samples based
on functionalized carbon nanotubes by
static head space gas chromatography mass
spectrometry, Anal. Method Environ. Chem.
J., 3 (2020) 17-26.
[74] L. Mohammadi, E. Bazrafshan, M.
Noroozifar, A. Ansari-Moghaddam, F.
Barahuie, D. Balarak, Adsorptive removal
of benzene and toluene from aqueous
environments by cupric oxide Nanoparticles:
kinetics and isotherm studies, Hindawi, J.
Chem., 2017 (2017) 206-219.
F. Murshed, M. A. Faris, R. Bayuaji, Review
on adsorption of heavy metal in wastewater
by using geopolymer, In proceedings of the
MATEC web of conferences, Ho Chi Minh,
Vietnam, 10-23, 2016.
[76] A. S. Mohammed, A. Kapri, R. Goel, Heavy
metal pollution: Source, impact, and remedies.
In biomanagement of metal contaminated
soils; Springer, Berlin/Heidelberg, Germany,
1–28, 2011.
[77] M. M. Hussain, J. Wang, I .Bibi, M. Shahid,
N. K. Niazi, J. Iqbal, I. A. Mian, S. M.
Shaheen,. S. Bashir, N. S. Shah, Arsenic
speciation and biotransformation pathways
algae, J. Hazard. Mater.,4 (2020) 12-27.
[78] C.Y. Lu, M.Y. Wey, Simultaneous removal
of VOC and NO by activated carbon
impregnated with transition metal catalysts
Technol., 88 (2007) 557–567.
[79] J. Taylor, C. Shrubsole, P. Symonds, I.
Mackenzie, M. Davies, Application of an
indoor air pollution metamodel to a spatially-
distributed housing stock, Sci. Total Environ.,
667 (2019) 390–399
[80] Burden of disease from the joint effects of
household and ambient air pollution, WHO:
105
Geneva, Switzerland, 2018.
[81] A. Molina, V. Escobar-Barrios, J. Oliva,
sensors, Synth. Met., 270 (2020) 116602.
[82] A. Chen, R. Liu, X. Peng, Q. Chen, J. Wu,
2D Hybrid Nanomaterials for Selective
Detection of NO2 and SO2 using light on and
off strategy, ACS Appl. Mater. Interfaces, 9
(2017) 37191–37200.
[83] L. Barelli, G. Bidini, L. Micoli, E. Sisani,
M. Turco, 13X Ex Cu zeolite performance
characterization towards H2S removal for
biogas use in molten carbonate fuel cells,
[84] Y. Belmabkhout, P.M. Bhatt, K. Adil, R.S.
Pillai, A. Cadiau, A. Shkurenko, G. Maurin,
G. Liu, W.J. Koros, M. Eddaoudi, Natural
tuned H2S and CO2 adsorption selectivity,
[85] H.Y. Zhang, C. Yang, Q. Geng, H.L. Fan,
B.J. Wang, M.M. Wu, Z. Tian, Adsorption
metal organic framework (MOF-199): An
experimental and simulation study, Appl.
Surf. Sci., 497 (2019) 143815
[86] S.T. Magwaza, L.S. Magwaza, A.O. Odindo,
A. Mditshwa, Hydroponic technology as
decentralised system for domestic wastewater
treatment and vegetable production in urban
agriculture: A review, Sci. Total Environ.,
698 (2020) 134154.
[87] H. Xiao, Q. Cheng, M. Liu, L. Li, Y. Ru,
D. Yan, Industrial disposal processes for
treatment of polychlorinated dibenzo-p-
dioxins and dibenzofurans in municipal solid
(2020) 12535.
[88] M.Y. Wey, C.H. Fu, H.H. Tseng, K.H.
Chen, Catalytic oxidization of SO2 from
catalysts supported on pre-oxidized activated
carbon, Fuel, 82 (2003) 2285–2290.
[89] O. Maass, P. Grundmann, Added-value
from linking the value chains of wastewater
treatment, crop production and bioenergy
production: A case study on reusing
wastewater and sludge in crop production in
Braunschweig (Germany), Resour. Conserv.
Recycl., 107 (2016) 195–211.
[90] J. M. Tobin, J. C. Roux, Mucor biosorbent
Water Res., 32 (1998) 1407–1416.
[91] V. Prigione, M. Zerlottin, D. Refosco, V.
Tigini, A. Anastasi, Varese, Chromium
autochthonous and allochthonous fungi,
Bioresour. Technol., 10 (2009) 2770–2776.
[92] C. Chen, B. Liang, A. Ogino, X. Wang,
M. Nagatsu, Oxygen functionalization
of multiwall carbon nanotubes by
microwaveexcited surface-wave plasma
treatment, J. Phys. Chem. C, 113 (2009)
7659–7665.
[93] K. H. Goh, T.T. Lim, Z. Dong, Application
of layered double hydroxides for removal of
oxyanions: A review, Water Res., 2 (2008)
1343–1368.
[94] L. Huang, M. He, B. Chen, B. Hu, Magnetic
Zr-MOFs nanocomposites for rapid removal
of heavy metal ions and dyes from water,
Chemosphere, 4 (2018) 435–444.
[95] D. Park, Y. S. Yun, J. M. Park, The past,
present, and future trends of biosorption,
Biotechnol. Bioprocess Eng., 15 (2010) 86–
102.
[96] H. Shirkhanloo, M. Osanloo, M. Ghazaghi,
H. Hassani, Validation of a new and cost-
effective method for mercury vapor removal
based on silver nanoparticles coating on
micro glassy balls, Atmos. Pollut. Res.,
(2017) 359-365.
[97] H. Shirkhanloo, A. Khaligh, H. Zavvar
Mousavi, A. Rashidi, Ultrasound assisted-
dispersive-ionic liquid-micro-solid phase
extraction based on carboxyl-functionalized
nanoporous graphene for speciation and
determination of trace mercury in water
samples, Microchem. J., 130 (2016) 245-254.
Review of pollutants in Environment Chemistry Ihenetu Stanley Chukwuemeka et al
106
Anal. Methods Environ. Chem. J. 4 (3) (2021) 80-106
[98] H. Shirkhanloo, A. Khaligh, HZ. Mousavi,
A. Rashidi, Ultrasound assisted-dispersive-
micro-solid phase extraction based on
bulky amino bimodal mesoporous silica
nanoparticles for speciation of trace
manganese (II)/(VII) ions in water samples,
Microchem. J., 124 (2015) 637–645.
[99] HZ. Mousavi, A.M. Rashidi, Ultrasound-
assisted dispersive solid phase extraction of
cadmium (II) and lead (II) using a hybrid
nanoadsorbent composed of graphene and
the zeolite clinoptilolite, Microchim. Acta,
182 (2015) 1263-1272.
[100] J. Rakhtshah, N. Esmaeili, A rapid
extraction of toxic styrene from water and
wastewater samples based on hydroxyethyl
immobilized on MWCNTs by ultra-
assisted dispersive cyclic conjugation-micro-
solid phase extraction, Microchem. J., 170
(2021) 106759.
[101] R. Ashouri, Dynamic and static removal of
benzene
liquid coated on MWCNTs by sorbent tube-
headspace solid-phase extraction procedure,
Int. J. Environ.Sci. Technol., 18 (2021)
2377–2390.
