Anal. Method Environ. Chem. J. 3 (2) (2020) 21-33
Separation and determination of mercury from nail and hair
in petrochemical workers based on silver carbon nanotubes
by microwave-assisted headspace sorbent trap
Daniel Soleymania, Sahar Zargarib and Ali Faghihi-Zarandia,*
a Occupational Health Engineering Department, Modeling in Health Research Center, Institute
for Futures Studies in Health,Kerman University of Medical sciences, Kerman, Iran
bSoftware Engineer, Statistical sciences and engineering, Department of Web development and software engineering,
Research Institute of Petroleum Industry, Tehran, Iran
ABSTRACT
In this work, the occupational analytical chemistry was developed
for determination of chronic exposure of mercury in nail and hair in
petrochemical workers (Age: 30-50, Men). By experimental procedure,
100 mg of hair and nail of workers was prepared by washing / grinding
and then the powder was dried in oven for 20 min at 95oC. 20 mg of hair
or nail samples added to reagents (HNO3/H2O2; 5:1) in polyethylene
tube (PET) of microwave digestion and the mercury in resulting
solution was removed with silver nanoparticles pasted on multi-walled
carbon nanotubes (Ag-MWCNTs) which were placed in head space of
separator. After microwave digestion for 25 min, the mercury vapor was
removed by Ag-MWCNTs as the headspace sorbent trap (HSST) under
hood conditions. Finally, the mercury in sorbent was online determined
by cold vapor atomic absorption spectrometry (CV-AAS) after heat
process at 250oC in presence of Ar gas. The capacity adsorptions of Ag-
MWCNTs and MWCNTs for mercury removal from air were obtained
205.4 mg g-1 and 63.7 mg g-1, respectively. The mean of mercury in nail
and hair in workers and healthy peoples was achieved (15.2±3.7 μg g-1;
11.6± 2.6 μg g-1) and (0.16±0.05 μg g-1; 0.24± 0.03 μg g-1), respectively
(RSD<5%). The validation of method was done by certied reference
material (CRM).
Keywords:
Mercury,
Nail and Hair,
Silver multi-walled carbon
nanotubes,
Microwave-assisted headspace
removal
ARTICLE INFO:
Received 29 Feb 2020
Revised form 17 Apr 2020
Accepted 14 May 2020
Available online 27 Jun 2020
* Corresponding Author: Ali Faghihi-Zarandi
Email: alifaghihi60@yahoo.com
https://doi.org/10.24200/amecj.v3.i02.99
1. Introduction
Mercury, as a trace heavy metal element, is the
only common metal which is liquid at ordinary
temperatures and has a high vapor pressure [1].
Atmospheric mercury is present in three forms:
metallic or elemental mercury (Hg0), oxidized or
inorganic mercury (Hg2+) and particulate-bound
mercury with organic materials such as methyl (R-
Hg) [2]. Each of these forms has different impacts
on health surveillance and requires different
countermeasures to avoid exposure. Hg0 is oxidized
to inorganic forms of Hg2+, when entering the
atmosphere. Elemental mercury in its gaseous form
is the main form of mercury in the atmosphere with
atmospheric lifetime of approximately 6–24 months
[3]. It is a pollutant of great concern due to its volatility,
toxicity, persistence, and bioaccumulation in the
environment and its neurotoxic impact on human
health [4,5]. Mercury vapors are well absorbed into
blood through the lungs (approximately 80%) and can
easily cross the blood-brain barrier as a lipid-soluble
substance in human body tissues such as brain and
Research Article, Issue 2
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
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22
renal [6]. Chlor-alkali factories using mercury metal
as a liquid electrode in the manufacturing of chlorine
(Cl2) and sodium hydroxide (NaOH) by electrolysis
release of the mercury vapor in air and so, it causes
to disease in workers by exposure of the workers to
mercury [7]. Chlor–alkali plants (CAP) which use
mercury (Hg) in electrolytic cell manufacture has
been identied as one of the main sources of Hg
pollution in environmental air. Although alternative
methods were established to replace the Hg-cell
process, many older plants are still in operation in
some undeveloped areas. In addition, many amounts
of mercury enter to environment by different
sources such as chemical factories, petrochemical
activity, volcanoes, forest res, and fossil fuels [8].
Bioaccumulation of mercury in the human body
changes the normal cell/tissues/organs and cause to
cancer. It can damage the physiological activities of
the human body especially in the brain and renal,
even at very low concentrations of mercury [9]. The
primary target for Hg exposure is the central nervous
system (CNS) and then, it can also damage many organ
systems such as liver and renal through its ephemeral
and residual systemic distribution [10] Finally, the
chronic mercury exposure can be damaged the cells
of kidney [11] and central nervous system (CNS)
[12]. In addition, the other organs/systems such as
the immune system, reproduction and cardiovascular
system can also be affected by mercury exposure
[13]. The mercury exposure has adverse health effect
in human body and can depend on the form of the
mercury, time and dose of exposure [14]. Acute, high-
dose exposure to elemental mercury vapor may cause
to pneumonitis. At low levels, the acute lung injury,
insomnia, headaches, disturbances in sensations and
changes in nerve responses is obtained and then, the
chronic inhalation cause to many problems include,
tremor, gingivitis, particularly irritability, depression,
short-term memory loss, fatigue, anorexia, and
sleep disturbance [15]. In the general population,
the total blood mercury concentration is due mostly
to the dietary intake of organic forms, particularly
methyl mercury and urinary mercury consists mostly
of inorganic mercury forms [15]. Several studies
identied a signicant positive association between
mercury in hair samples and hypertension (blood
pressure); whereby the exposure dose is an important
factor for determining the toxic effects of mercury
[16]. Hair mercury concentration as a biomarker
of organic and inorganic mercury exposure can be
provided the information over a denable period
of time, based upon sequential analyses of hair
segments, to represent both the magnitude and timing
of past exposure. However, the mercury analysis in
hair have two problems. The rst concerns the origin
of the measured elements, and the second concerns
the biological signicance that may be given to the
level of the elements. Unlike hair, total blood mercury
levels also include inorganic mercury, which may
be of importance in certain contexts. It is generally
considered the appropriate indicator of the absorbed
dose. Urinary mercury concentrations are widely used
as a biomarker of mercury exposure from elemental or
inorganic mercury [17]. Note, the inorganic mercury
can be changed to organic forms by high concentration
of mercury or chronic exposure of mercury. It is
very important to develop a novel analytical method
for determination of heavy metals in environment
and biological samples for monitoring the severity
of heavy metal pollution. At the present time, the
most well-known methods for detecting heavy
metals are atomic absorbance spectrometry (AAS)
[18], atomic uorescence spectrometry (AFS) [19],
electrochemical analysis, inductively coupled plasma
(ICP) [20], high performance liquid chromatography
(HPLC) [21] and capillary electrophoresis [22].
However, these methods generally need a sample
preparation or extraction procedure [23]. Recently,
the cold vapor atomic absorption spectrometry (CV-
AAS) was used as a favorite analytical technique for
mercury analyses in various types of samples [24], but
it has been necessary to develop with preconcentration
methods that allow mercury determination at ultra-
trace levels [25]. Liquid-liquid extraction/micro
extraction (LLE/LLME) and solid-phase extraction/
micro solid-phase extraction (SPE&MSPE) are the
most commonly employed methods to achieve the
separation and preconcentration of metal ions [26-28].
In this study, the chronic exposure of mercury in nail
and hair of petrochemical workers was determined
Anal. Method Environ. Chem. J. 3 (2) (2020) 21-33
23
by microwave-assisted headspace removal procedure
(MAHR). By procedure, the microwave based on
silver nanoparticles passed on multi-walled carbon
nanotubes (Ag-MWCNTs) was used as head space
removal and mercury concentration was determined
by CV-AAS.
2. Experimental
2.1. Instrumental
Mercury was measured by an atomic absorption
spectrometer (AAS, GBC 932, Australia) equipped
with a ow injection cold vapor accessory (FI-CV).
The background correction with a deuterium-lamp
and hollow-cathode lamp of mercury was used. The
circulating cooling unit (CCU) caused to generation
of vapour of mercury in cold conditions. NaBH4 /
NaOH or SnCl2/HCl was used as reduction agents
for generating of mercury hydride which was moved
to liquid –gas separator by Ar. The conditions of
FI-CVAAS were shown in Table 1. The pH ranges
in liquid phase were adjusted and determined by a
Metrohm pH meter (744, Switzerland). The multi-
wave microwave system (MMS, Anton Paar 3000,
Austria) was used for digestion of hair and nail
samples which was converted the organic mercury
to inorganic mercury. Anton Paars 8-position rotor
(8SXQ80) and respective reaction vessels individually
equipped with variable temperature and ultraviolet
(UV) radiations. The temperature and pressure of
MMS were 220°C and 35 bar, respectively.
2.2. Reagents
All reagents with high purity as an analytical
grade were purchased from Merck (Darmstadt,
Germany). All samples were prepared with the
deionized water (DW) from Millipore water system
(USA). The standard stock solution of inorganic
mercury (1000 mg L-1 Hg(II) in 1% nitric acid) was
purchased from Fluka, Switzerland. The working
standard solutions were prepared daily by diluting
of standard solutions with DW. The solutions
were freshly prepared and stored just in a fridge
(4 °C) to prevent decomposition. First, 0.6% (w/v)
NaBH4 solution was prepared daily by dissolving
in 0.5% (w/v) sodium hydroxide (NaOH) and used
as a reducing agent. The glassware and plastics of
laboratory were cleaned by nitric acid (15%, v/v)
for at least 12 h and then washed with DW. Silver
nitrate, ammonia, formalin, and ethanol were
purchased from Merck Company (Germany).
2.3. Synthesis of AgNPs-MWCNTs
The silver nanoparticles passed on MWCNTs have
prepared. First, the mixture of MWCNTs (10 mg)
in 100 mL of DW solution was prepared and then,
0.3 g of T-X100 as a surfactant was dispersed in
mixture at 300 rpm stirring speed. The 0.5 g of
silver nitrate was added to the mixture (MWCNTs/
AgNO3/TX-100/DW) without heat in same stirring
speed (300 rpm). Finally, 2 mL of the ammonia
solution was added to above solution and diluted
with DW up to 0.5 L by stirring at 15 minute. Then,
12 mL of formalin as a reducing agent was added
to product in 5 min and by increasing the speed of
stirring (600-800 rpm), the AgNPs (20-100 nm)
were coated on the MWCNTs. For cleaning of the
MWCNTs from CH2O and NH3, the product was
washed with DW for 10 times. For preventing of
silver oxidation, the product (AgNPs-MWCNTs)
washed with Ethanol or increasing temperature up
to 180oC.
2.4. Procedure
As Figure 1, 20 mg of hair or nail samples and
reagents (HNO3 / H2O2; 5:1) was put into PET of
microwave digestion at UV/@220oC for 30 min.
Table 1. The conditions of mercury determination by
FI-CVAAS with closed cell
Features Value
Linear range 0.5-65 μg L-1
Working range 0.5-150 μg L-1
Wavelength 253.7 nm
Lamp current 4.0 mA
Slit 0.5 nm
Mode Peak Area surface
HCl carrier solution 37% 3.4 mol L-1
NaBH4 reducing agent, % (m/v) 0.6 (0.5% NaOH)
Argon ow rate 15.0 mL min-1
Sample ow rate 4.0 mL min-1
Reagent ow rate mL min-1
Silver carbon nanotubes for measuring mercury Daniel Soleymani et al
24
After digestion, the resulting solution was diluted
with DW up to 10 mL mixed with reducing reagents
(NaBH4/NaOH) in mixer. Then, the hydride form of
mercury in liquid phase was generated by reaction
loop before moved to separator by owrate of 100 ml
min-1. As ultra-trace mercury (sub ppb), the mercury
was preconcentrated by Ag-MWCNTs trap in head
space of separator. Finally, the concentration mercury
was online determined by closed cell FI-CV-AAS
after thermal desorption by heat accessory at 185oC
in presence of Ar gas. The peak area of absorption
was calculated as concentration of mercury in nail
or hair samples by Avanta software of FI-CV-AAS.
The conditions of procedure were shown in Table 2.
Fig.1. Determination mercury in nail and hair based on Ag-MWCNTs by HSST method
Table 2. The conditions of the headspace sorbent trap (HSST) method in nail, hair and water samples
by Ag-MWCNTs sorbent
Parameter Nail/Hair sample Water sample
PFa 32.2 35.1
LODb (n=10, ng L-1) 5.3 4.5
RSDc (%) 2.4 1.9
Linear range (μg L−1) 0.015– 2.1 0.013-1.85
Working range(μg L−1) 0.015– 4.7 0.013-4.4
Correlation coefcient 0.9991 0.9995
a Preconcentration factor, b Limit of detection,
c Relative standard deviation.
Anal. Method Environ. Chem. J. 3 (2) (2020) 21-33
The Ethical Committee of Kerman University of Medical Science (E.C.:IR.KMU.REC.1400.143) was
approved the project of human nail and hair samples which was considered based on guiding physicians in
human body research in human tissue by the world medical association declaration of Helsinki.
25
3. Results and Discussion
As chronic exposure of mercury in nail and hair
in petrochemical workers, the novel method based
on Ag-MWCNTs sorbent was used for mercury
determination by microwave-headspace sorbent
trap (MW-HSST) procedure. For optimization
recovery, the parameters such as, temperature,
owrate, adsorption capacity was studied. On the
other hand, validation of proposed method was
achieved based on spiking samples and Microwave
digestion coupled to gold MC-3000 as ultra-trace
analyzer of mercury (ppt). Based on results,
the recovery of Ag-MWCNTs and MWCNTs
sorbents was obtained 38.5 and 98.3, respectively.
The recoveries in Ag-MWCNTs and MWCNTs
sorbents were determined by MW-HSST procedure
(equation I). Furthermore, the adsorption capacity
of sorbents was considered by equation of II.
(Eq. I)
(Eq. II)
As equation I, a is the primary concentration of
mercury and b is the nal concentration of mercury,
the adsorption capacity (mg g-1) was shown in
equation of II and and (mg L-1) are before and
after adsorption of mercury concentration by Ag-
MWCNTs, V is the air volume as owrate and (g)
is the mass of Ag-MWCNTs.
3.1. Characterization
The specic surface area (SBET) of Ag-MWCNT
and MWCNTs were obtained from the BET
equation at 20oC. Decreasing of BET surface area of
Ag-MWCNT in comparison with initial MWCNT
was due to the grafting of silver nanoparticles on
walls of MWCNTs.
The SEM micrographs of MWCNTs and Ag-
MWCNTs were shown in Figure 2a and 2b. The
diameter of MWCNTs and Ag-MWCNTs is
approximately between 30-100 nm. The XRD
patterns of MWNTs and Ag-MWCNTs were shown
in Figure 3. The TEM micrographs (Germany,
Philips CM30, 250 kV) showed the morphology
of the MWCNTs and Ag-MWCNTs particles.
Nano particles of MWNTs and Ag-MWCNTs were
dissolved in ethanol by shaking for 15 min and a
drop of the ethanol was used by TEM instrument.
The similar TEM micrographs for MWNTs and
Ag-MWCNTs were obtained about 40 nm (Fig. 4a
and 4b).
Fig. 2a. The SEM of MWCNTs.
Fig. 2b. The SEM of Ag-MWCNTs.
Silver carbon nanotubes for measuring mercury Daniel Soleymani et al
26
Fig. 3. The XRD of MWCNTs and Ag-MWCNTs
Fig. 4a. The TEM of MWCNTs. Fig. 4b. The TEM of Ag-MWCNTs
Anal. Method Environ. Chem. J. 3 (2) (2020) 21-33
27
3.2. Effect of temperature
The effect of temperature for absorption and
desorption mercury by Ag-MWCNTs sorbent was
investigated. The temperatures between 20-2000C
was studied for procedure. As results, the recovery
of Ag-MWCNTs and MWCNTs was decreased in
high temperature and the mercury can be desorbed
from Ag-MWCNTs and MWCNTs at 185oC and
more than 80oC. The results showed, the optimum
temperature for adsorption and desorption mercury
from Ag-MWCNTs sorbent was obtained 25-35oC
and 185oC (Fig. 5).
At temperature more than 35oC, the removal
efciency of mercury by Ag-MWCNTs were
decreased. Temperature had more effected on
mercury removal by Ag-MWCNTs as compared to
humidity.
3.3. Effect of ow rate
The main factor for adsorption of mercury on Ag-
MWCNTs sorbent was depended on owrate of Argon
gas which was caused to increase interaction Hg with
Ag as amalgamation form (Ag-Hg). As optimized
conditions for removal of mercury by headspace
sorbent trap (HSST) method, the ow rates must be
evaluated. So, the ow rates between 50 - 500 mL min-
1 were optimized for Ag-MWCNTs and MWCNTs at
room temperature. The ow rate was determined by
a rotameter accessory in room temperature. In high
and low owrate, the rate of adsorption was reduced
and increased, respectively. The results showed
that maximum recovery for mercury removal was
achieved by Ag-MWCNTs at owrate 100 ml min-1.
Figure 6 showed the effects of ow rate on the removal
efciency of mercury by HSST method.
Fig. 5. The effect of temperature on desorption mercury from
Ag-MWCNTs and MWCNTs sorbents by HSST method.
Fig. 6. The effect of ow rate on removal of mercury vapor from liquid
phase by Ag-MWCNTs and MWCNTs sorbents
Silver carbon nanotubes for measuring mercury Daniel Soleymani et al
28
3.4. Adsorption capacity
In this study, the adsorption capacity of mercury
by Ag-MWCNTs, and MWCNTs in batch system
has obtained 205.4 mg g-1, 63.7 mg g-1, respectively
which was shown in Figure 7. The closed special
vial (10 mL) was used with 5 mL of liquid standard
mercury value (100 mg), 0.2 g of Ag-MWCNTs,
and MWCNTs sorbents in head space of vial and
reducing agents which was added by syringe with
beside input port. After 5, 10, 15, 20 min, the mercury
in sorbent determined by CV-AAS. The results
showed us, the maximum removal was achieved by
Ag-MWCNTs after 15 min. By procedure, the nal
concentration in sorbent was obtained 41.1 mg of
mercury after thermal desorption.
3.5. Validation
The accurate and precise results for mercury
determination in nail /hair are important factor for
human samples. So, the mercury results based on
Ag-MWCNTs must be validated by MW-HSST
procedure. First, the different concentration of
standard mercury solutions from 0.5 to 5 μg L-1 was
prepared. For validation, the different concentrations
of mercury were used for spiking of nail, hair and
water samples by Ag-MWCNTs sorbents (Table
3). The removal efciency of sorbents based on
MW-HSST was evaluated. For method validation
ICP analyzer was used for nail and hair samples
after sample digestion (Table 4). In addition, the
removal efciency of mercury in water and gas
phase by different sorbents was compared to MW-
HSST procedure (Table 5). According to table5,
the Ag-MWCNTs have more efficiency than other
sorbents. The Ethical Code for human nail and
hair samples approved by Kerman University of
Medical Science (E.C.: IR.KMU.REC. 1400.143).
Fig. 7. The absorption capacity of mercury by Ag-MWCNTs and MWCNTs sorbents by HSST method
Table 3. Validation of MW-HSST procedure for total mercury determination in nail, hair and water samples by
spiking of real samples
Sample Added (μg L−1)Found (μg L−1) Recovery(%)
Human Nail ------ 1.43 ± 0.05 ------
1.5 2.91 ± 0.12 98.6
Human Nail ------ 0.17 ± 0.01 ------
0.2 0.36 ± 0.02 95.0
Human Hair ------ 1.98 ± 0.08 ------
2.0 4.02 ± 0.17 102
Human Hair ------ 0.55 ± 0.02 ------
0.5 1.03 ± 0.04 95.8
Well Water ------ 0.38 ± 0.01 ------
0.5 0.86 ± 0.03 96.0
Anal. Method Environ. Chem. J. 3 (2) (2020) 21-33
29
3.6. Discussion
Krawczyk et al was used TiO2 nanoparticles (NPs)
as adsorbent for preconcentration and determination
of mercury species (Hg total, Hg2+ and CH3Hg+) in
biological, environmental and water samples. The
mercury extracted based on ultrasound-assisted
dispersive micro solid-phase extraction (USA
DMSPE) and determined by cold vapor atomic
absorption spectrometry (CV AAS). The detection
limit of the method for Hg2+ and relative standard
deviations (RSD%) was obtained 4 ng L−1 and
4–20%, respectively. The mercury was separated
from liquid phase with 10 mg of TiO2 at pH 7.5[39].
In addition, Ma et al showed that the mercaptopropyl
Table 4. ICP analyzer was used for validation of proposed method for mercury
determination in nail and hair samples after sample digestion
Sample ICP-MS (μg L−1)Added (μg L−1)Found (μg L−1) Recovery (%)
Nail 1.24 ± 0.03 ------ 1.20 ± 0.05 96.8
------ 1.0 2.17 ± 0.09 97.0
Hair 0.52 ------ 0.54 ± 0.03 103.8
------ 0.5 1.02 ± 0.04 96.0
Table 5. Comparing of Ag-MWCNTs based on MW-HSST procedure with different sorbents
by published method
ReferenceRecovery
Absorption Capacity
( mg g−1)
TechniqueMatrixSorbents
[29]----0.70–3.83 AdsorptionReal waters
Solid-phase extraction
with multiwalled carbon
nanotubes
[30]----9.3 AmalgamationFlue gasesAg-CNT
[31]98%91.8
Amalgamation/
SPGE
Air/Articial air
Silver nano particles/
MGBs
[32]35.3%----
Microwave
assisted catalytic
Flue gas
Mn/zeolite catalyst
[33]98.5%--------
Gas Porous carbon-supported
CuCl2
[34]----497.84 (μg·g–1)Adsorption
Coal Combustion
Fuel Gas
Nano-ZnS
[35]75.58%----Chemisorption Flue gasnano-ceramic
[36]97%145 (μmol g-1) Adsorption Natural Waters Au NP–Al2O3
[37]96%376.3 ----Aqueous solutions
Silver/quartz
nanocomposite
[38]75%----ComplexationWater
magnetic nanoparticles
coated with yam peel
biomass (MNP-YP)
[40]96.477.0
SPE/Anodic
Stripping
Voltammetry
WaterReduced graphene oxide
This work98.8205.4MW-HSSTNail/HairAg-MWCNTs
Silver carbon nanotubes for measuring mercury Daniel Soleymani et al
30
trimethoxysilane (MPTS) modied on Fe3O4@SiO2
as a magnetic nanoparticles (MNPs) can used for
the speciation of mercury in environmental water
and human hair samples. The characterization of
(MPTS-MNPs) was obtained by Fourier transform
infrared spectrometer (FT-IR), transmission
electron microscope (TEM) and vibrating sample
magnetometer (VSM). In the optimized conditions,
the limits of detection (LOD) for CH3Hg+ and total
Hg were achieved 1.6 and 1.9 ng L-1, respectively.
This method successfully applied for the speciation
of CH3Hg+ and Hg2+ in water and hair samples [40].
A novel Fe3O4@SiO2@polythiophene magnetic
nanocomposite was synthesized by Abolhasani
et al. They could determine the Hg(II) ions in sea
food samples. After sample digestion, the mercury
was determined by cold vapor atomic absorption
spectrometry (CV AAS). Under the optimum
condition, the LOD (20 ng L−1) and RSD% (9.2 %)
were obtained. The capacity adsorption of Fe3O4@
SiO2@polythiophene magnetic nanocomposite
was 59 mg g−1 which was lower than our proposed
method base on Ag-MWCNTs (184.3 mg g-1)
[41]. In other study, Akbar et al was reported a
SPE method based on mGO@SiO2@2-MPATD
nanocomposite for determination of mercury in the
water and seafood samples. The characterization
was obtained by FT-IR, SEM, and elemental
analysis techniques. After adsorption and elution
steps, the concentration of Hg (II) was measured
by CV-AAS. Under the optimized conditions,
the limit of detection was 8 ng L−1. The capacity
adsorption of mGO@SiO2@2-MPATD was
obtained 236 mg g−1 which was higher than
proposed method by Ag-MWCNTs [42]. Also,
Krawczyk et al introduced the silver nanoparticles
(AgNPs) as solid sorbent for preconcentration and
determination of Hg2+ ions in water samples. The
limit of detection and RSD% was achieved 5 ng L-1
and 6-11%, respectively [43].
4. Conclusions
In this study, a robust analytical method based
on microwave coupled to headspace sorbent trap
(HSST) was developed for determination mercury
in nail and hair in petrochemical male workers
aged 30 to 60 years. Results showed the capacity
adsorptions of Ag-MWCNTs and MWCNTs for
mercury removal from the air were obtained 205.4
mg g-1 and 63.7 mg g-1, respectively. It means
that mercury removal from the air was increased
dramatically by silver nanoparticles pasted on
multi-walled carbon nanotubes. After nail/hair
digestion, the mercury in liquid phase converted
to hydride form (HgH2) and captured by silver
nanoparticles on MWCNTs as a sorbent trap in
head space of separator. The LOD and LOQ of
proposed procedure was obtained 5 ng L-1 and 15
ng L-1, respectively. Also, the mean of mercury
in nail and hair in workers and control group was
achieved (15.2 ±3.7 μg g-1; 11.6 ± 2.6 μg g-1) and
(0.16 ± 0.05 μg g-1; 0.24 ± 0.03 μg g-1), respectively
(RSD<5%). Regardless of the interfering factors,
the difference between these values is due to high
exposure with mercury.
5. References
[1] H. Satoh, Occupational and environmental
toxicology of mercury and its compounds,
Industrial. Health, 38 (2000) 153-164.
[2] B. Zhao, H.H. Yi, X.L. Tang, Q. Li, D.D. Liu,
F.Y. Gao, Copper modied activated coke for
mercury removal from coal-red ue gas,
Chem. Eng. J., 286 (2016) 585-593.
[3] UN Environment Document Repository,
Global mercury modelling: update of
modelling results in the global mercury
assessment 2013. https://wedocs.unep.org/
handle/20.500.11822/13772 , 2015.
[4] Y.S. Gao, Z. Zhang, J.W. Wu, L.H. Duan,
A. Umar, L.Y. Sun, Z.H. Guo, Q. Wang, A
critical review on the heterogeneous catalytic
oxidation of elemental mercury in ue gases,
Environ. Sci. Technol., 47 (2013) 10813–
10823.
[5] S.L. Tang, L.N. Wang, X.B. Feng, Z.H. Feng,
R.Y. Li, H.P. Fan, K. Li, Actual mercury
speciation and mercury discharges from coal-
red power plants in Inner Mongolia, northern
China, Fuel, 180 (2016) 194–204.
Anal. Method Environ. Chem. J. 3 (2) (2020) 21-33
31
[6] M. Sakamoto, N. Tatsuta, K. Izumo, P.T.
Phan, L.D. Vu, M. Yamamoto, M. Nakamura,
K. Nakai, K. Murata, Health impacts
and biomarkers of prenatal exposure to
methylmercury: Lessons from Minamata,
Japan, Toxic., 6 (2018).
[7] G.J. Zagury, C.-M. Neculita, C. Bastien,
L. Deschênes, Mercury fractionation,
bioavailability, and ecotoxicity in highly
contaminated soils from chlor-alkali plants,
Environ. Toxicol. Chem., 25 (2006) 1138-
1147.
[8] C. Feng, Z. Zayas, L. Lima, S. Olivares, D. De
La Rosa, S. Berail, E. Tessier, F. Pannier, D.
Amouroux, Assessment of Hg contamination
by a chlor-alkali plant in riverine and coastal
sites combining Hg speciation and isotopic
signature (Sagua la Grande River, Cuba),
J. Hazard. Mater., 371 (2019) 558-65.
[9] L.-n. Liang, J.-b. Shi, B. He, G.-b. Jiang, C.-
g. Yuan, Investigation of methyl mercury
and total mercury contamination in mollusk
samples collected from Coastal sites along the
Chinese Bohai sea, J. Agric. Food. Chem., 51
(2003) 7373-7378.
[10] C. Gundacker, S. Fröhlich, K. Graf-
Rohrmeister, B. Eibenberger, V. Jessenig, D.
Gicic, S. Prinz, K.J. Wittmann, H. Zeisler, B.
Vallant, A. Pollak, P. Husslein, Perinatal lead
and mercury exposure in Austria, Sci. Total.
Environ., 408 (2010) 5744-5749.
[11] S.E. Orr, C.C. Bridges, Chronic kidney disease
and exposure to nephrotoxic metals, Int. J.
Mol. Sci., 18 (2017).
[12] H. Lohren, J. Bornhorst, R. Fitkau, G. Pohl,
H.-J. Galla, T. Schwerdtle, Effects on and
transfer across the blood-brain barrier in
vitro—Comparison of organic and inorganic
mercury species, BMC. Pharmacol. Toxicol.,
17 (2016) 63.
[13] G. Genchi, M.S. Sinicropi, A. Carocci, G.
Lauria, A. Catalano, Mercury exposure and
heart diseases, Int. J. Environ. Res. Public.
Health, 14 (2017) 74.
[14] F. Ruggieri, C. Majorani, F. Domanico, A.
Alimonti, Mercury in children: current state
on exposure through human biomonitoring
studies, Int. J. Environ. Res. Public. Health,
14 (2017).
[15] Centers for Disease Control and Prevention,
National biomonitoring program: mercury,
2017. https://www.cdc.gov/biomonitoring/
Mercury_BiomonitoringSummary.html/
[16] X.F. Hu, K. Singh, H.M. Chan, Mercury
exposure, blood pressure, and hypertension:
A systematic review and dose-response meta-
analysis, Environ. Health. Perspect., 126
(2018) 076002.
[17] L.T. Budnik, L. Casteleyn, Mercury pollution
in modern times and its socio-medical
consequences, Sci. Total. Environ., 654
(2019) 720-734.
[18] M.A. Kamyabi, A. Aghaei, A simple and
selective approach for determination of trace
Hg (II) using electromembrane extraction
followed by graphite furnace atomic
absorption spectrometry, Spectrochim. Acta
Part B: At. Spect., 128 (2017) 17-21.
[19] S.L.C. Ferreira, J.P. dos Anjos, C.S.A.
Felix, M.M. da Silva Junior, E. Palacio, V.
Cerda, Speciation analysis of antimony in
environmental samples employing atomic
uorescence spectrometry–Review, Trends.
Anal. Chem., 110 (2019) 335-343.
[20] M.-L. Lin, S.-J. Jiang, Determination of As,
Cd, Hg and Pb in herbs using slurry sampling
electrothermal vaporisation inductively
coupled plasma mass spectrometry, Food.
Chem., 141 (2013) 2158-2162.
[21] M. Thirumalai, S.N. Kumar, D. Prabhakaran,
N. Sivaraman, M.A. Maheswari, Dynamically
modied C18 silica monolithic column for
the rapid determinations of lead, cadmium
and mercury ions by reversed-phase high-
performance liquid chromatography, J.
Chromatogr. A, 1569 (2018) 62-69.
[22] S. Wang, X. Song, J. Hu, R. Zhang, L. Men,
M. Wei, T. Xie, J. Cao, Direct speciation
analysis of organic mercury in sh and kelp
by on-line complexation and stacking using
Silver carbon nanotubes for measuring mercury Daniel Soleymani et al
32
capillary electrophoresis, Food. Chem., 281
(2019) 41-48.
[23] Y. Wu, X. Wen, Z. Fan, An AIE active pyrene
based uorescent probe for selective sensing
Hg2+ and imaging in live cells, Spectrochim.
Acta. A. Mol. Biomol. Spec., 223 (2019)
117315.
[24] A.A. Elezz, H. Mustafa Hassan, H. Abdulla
Alsaadi, A. Easa, S. Al-Meer, K. Elsaid,
Z.K. Ghouri, A. Abdala, Validation of total
mercury in marine sediment and biological
samples, using cold vapour atomic absorption
spectrometry, Method. Protoc., 1 (2018) 31.
[25] F. Mercader-Trejo, R. Herrera-Basurto,
E.R. de San Miguel, J. de Gyves, Mercury
determination in sediments by CVAAS after
on line preconcentration by solid phase
extraction with a sol-gel sorbent containing
CYANEX 471X, Int. J. Environ. Anal. Chem.,
91 (2011) 1062-1076.
[26] V. Camel, Solid phase extraction of trace
elements, Spectrochim. Acta. Part. B: At.
Spec., 58 (2003) 1177-1233.
[27] A.E. Visser, R.P. Swatloski, S.T. Grifn,
D.H. Hartman, R.D. Rogers, Liquid-liquid
extraction of metal ions in room temperature
ionic liquids, Sep. Sci. Technol., 36 (2001)
785-804.
[28] W.I. Mortada, I.M.M. Kenawy, Y.G. Abou
El-Reash, A.A. Mousa, Microwave assisted
modication of cellulose by gallic acid and
its application for removal of aluminium from
real samples, Int. J. Biol. Macromol., 101
(2017) 490-501.
[29] A.H. El-Sheikh, Y.S. Al-Degs, R.M. Al-
As’ad, J.A. Sweileh, Effect of oxidation and
geometrical dimensions of carbon nanotubes
on Hg(II) sorption and preconcentration from
real waters, Desalination, 270 (2011) 214-220.
[30] G. Luo, H. Yao, M. Xu, X. Cui, W. Chen,
R. Gupta, Z. Xu, Carbon Nanotube-Silver
Composite for Mercury Capture and Analysis,
Energ. Fuels, 24 (2010) 419-426.
[31] 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., 8 (2017) 359-365.
[32] Z. Wei, Y. Luo, B. Li, Z. Cheng, J. Wang, Q.
Ye, Microwave assisted catalytic removal of
elemental mercury from ue gas using Mn/
zeolite catalyst, Atmos. Pollut. Res., 6 (2015)
45-51.
[33] F. Shen, J. Liu, Y. Dong, D. Wu, C. Gu, Z.
Zhang, Elemental mercury removal from
syngas by porous carbon-supported CuCl2
sorbents, Fuel, 239 (2019) 138-144.
[34] H. Li, L. Zhu, J. Wang, L. Li, K. Shih,
Development of nano-sulde sorbent for
efcient removal of elemental mercury from
coal combustion fuel gas, Environ. Sci.
Technol., 50 (2016) 9551-9557.
[35] T. Zhu, W. Jing, X. Zhang, W. Bian, Y. Han,
T. Liu, Y. Hou, Z. Ye, Gas-phase elemental
mercury removal by nano-ceramic material,
Nanomater. Nanotechnol., 10 (2020)
1847980419899759.
[36] S.-I. Lo, P.-C. Chen, C.-C. Huang, H.-T.
Chang, Gold nanoparticle–aluminum oxide
adsorbent for efcient removal of mercury
species from natural waters, Environ. Sci.
Technol., 46 (2012) 2724-2730.
[37] R.S. El-Tawil, S.T. El-Wakeel, A.E. Abdel-
Ghany, H.A.M. Abuzeid, K.A. Selim, A.M.
Hashem, Silver/quartz nanocomposite as an
adsorbent for removal of mercury (II) ions
from aqueous solutions, Heliyon, 5 (2019)
e02415.
[38] W. Marimón-Bolívar, L. Tejeda-Benítez, A.P.
Herrera, Removal of mercury (II) from water
using magnetic nanoparticles coated with
amino organic ligands and yam peel biomass,
Environ. Nanotechnol. Monit. Manage., 10
(2018) 486-493.
[39] M. Krawczyk, E. Stanisz, Ultrasound-assisted
dispersive micro solid-phase extraction with
nano-TiO2 as adsorbent for the determination
of mercury species, Talanta, 161 (2016) 384-
391.
[40] S. Ma, M. He, B. Chen, W. Deng, Q. Zheng, B.
Anal. Method Environ. Chem. J. 3 (2) (2020) 21-33
33
Hu, Magnetic solid phase extraction coupled
with inductively coupled plasma mass
spectrometry for the speciation of mercury in
environmental water and human hair samples,
Talanta, 146 (2016) 93-99.
[41] J. Abolhasani, R. Hosseinzadeh Khanmiri, M.
Babazadeh, E. Ghorbani-Kalhor, L. Edjlali,
A. Hassanpour, Determination of Hg(II)
ions in sea food samples after extraction and
preconcentration by novel Fe3O4@SiO2@
polythiophene magnetic nanocomposite,
Environ. Monit. Assess., 187 (2015) 554.
[42] M. Akbar, M. Manoochehri, An efcient
2-mercapto-5-phenylamino-1,3,4-thiadiazole
functionalized magnetic graphene oxide
nanocomposite for preconcentrative
determination of mercury in water and seafood
samples, Inorg. Chem. Commun., 103 (2019)
37-42.
[43] M. Krawczyk, E. Stanisz, Silver nanoparticles
as a solid sorbent in ultrasound-assisted
dispersive micro solid-phase extraction
for the atomic absorption spectrometric
determination of mercury in water samples,
J. Anal. At. Spectrom., 30 (2015) 2353-2358.
Silver carbon nanotubes for measuring mercury Daniel Soleymani et al