Research Article, Issue 4

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

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1. Introduction used to make various products including, alkaline

nickel-cadmium batteries, paints, alloys, plastics,

electroplating protective coatings, solders, rods,

television screens, lasers, pesticides, cosmetics and

barrier in nuclear process [1, 2, 4-6]. Cadmium is

an important industrial and environmental pollutant

because it is widely used in many industrial activities

(welding, smelting, mining, refining, soldering

and etc.) [1, 2, 7]. So, many employments are in

Cd exposure pollution. Approximately 512,000

workers in the United States have may a cadmium

exposure in each year [8]. Cadmium is one heavy

metal because relatively high density and its toxic

effects even at low concentration. Cadmium has

Kian Azami a, Mehdi Aliomrani b and Mostafa Dehghani Mobarake C,d,*

a Faculty of Pharmacy, Department of Toxicology Pharmacology, Tehran University of Medical Science, Tehran, Iran

b Department of Toxicology and Pharmacology, School of pharmacy, Isfahan University of Medical Sciences (IUMS), Isfahan, Iran

C Energy Technology Research Division, Research Institute of Petroleum Industry (RIPI), Tehran, Iran

d Department of Chemistry, University of Siegen, North Rhine Westphalia, Adolf-Reichwein-Straße 2, 57076, Siegen, Germany

Cadmium separation in human biological samples based on

captopril-ionic liquid paste on graphite rod before determination

by electrothermal atomic absorption spectrometry

Different chemical factories release toxic heavy

metals such cadmium, lead and mercury in air,

water, soil and also, it slowly enter to tissues of

plants and animals by vary sources of erosion and

abrasion of soils, forest fires and volcanic eruptions

[1-3]. Cadmium with special properties such as,

low melting temperature, corrosion resistance,

rapid ion electrical exchange activity, high

electrical and thermal conductivity can be used

in battery factories [2]. Due to these properties is

*Corresponding Author: Mostafa Dehghani Mobarake

E-mail: modeg128@yahoo.de

DOI: https://doi.org/10.24200/amecj.v2.i04.84

A R T I C L E I N F O:

Received 19 Aug 2019

Revised 24 Oct 2019

Accepted 6 Nov 2019

Available online 25 Dec 2019

Keywords:

Cadmium

Human samples

Captopril

Ionic liquid

Micro graphite rod

Micro solid phase extraction

A B S T R A C T

A mixture of captopril nanoparticles (CAP-NPs) and ionic liquid (IL,

[HMIM] [PF6]) paste on micro graphite rod (CAP-IL-MGR) and was

used for separation cadmium in human serum and urine samples by

micro solid phase extraction (μ-SPE). 0.01 g of CAP-NPs and 0.1 g

of [HMIM] [PF6] mixed with 1 mL of acetone and mixture passed

physically on micro graphite rod (MGR) at 55oC. Then, the graphite

probe placed on 10 mL of human biological samples with 5 min of

sonication, then cadmium ions complexed by thiol group of captopril

(CAP-SH) at pH=5.5. The cadmium ions on micro probe were back

extracted with 0.25 mL of nitric acid (0.5 M) which was diluted with

DW up to 0.5 mL and finally, the cadmium concentration determined

by ET-AAS. By optimizing of amount of captopril, the absorption

capacity and recovery were obtained 132.4 mg g-1 and more than

96%, respectively. The limit of detection (LOD), linear range (LR)

and enrichment factor (EF) were achieved 2 ngL-1, 0.01-0.35 μg L-1

and 19.7, respectively (RSD %<5%). The validation was done by

certified reference material (CRM, NIST) and ICP-MS analysis.

Cadmium analysis by captopril-ionic liquid Mostafa Dehghani Mobarake et al

Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 71-81

Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)

received considerable concern because its potential

accumulation in the environment and in living

organisms leading to long term toxic effects as a

non-essential element [9-12]. It is classified as a

human carcinogen by the north Carolina national

toxicology program (NTP), international agency

for research on cancer, (IARC), occupational

safety and health administration (OSHA) and

national institute of occupational safety and health

(NIOSH) [2, 6, 10, 13, 14]. Cadmium occupational

exposure to occurs primarily via respiratory

tract[15] or ingestion and absorbed by the body

and usually connected to metallothionein [4].

Cadmium mainly store in the liver and kidneys,

but to a lesser degree rest stored throughout other

organs of the body [2, 4, 16]. Toxic effects of Cd

depend on enter rout, quantity, rate of exposure

[4]. The values NIOSH and OSHA standard

for Cd exposure ceiling limit is lowest feasible

concentration and 0.005 mg m-3 respectively

[17]. Long-term exposures to low levels of can

result in renal disease but short-term Exposures

to high levels of cadmium liver accumulation and

hepatocellular damage. Exposures to cadmium

also can produce many health effects such as lung

irritation, testicular damage, pulmonary edema,

renal, hepatic dysfunction, multiple sclerosis (MS)

and osteomalacia and in some cases death. Various

studies reported correlation between occupational

Cd exposure and lung cancer and other cancers

such as the prostate, renal, liver, hematopoietic

system, urinary bladder, pancreatic, stomach and

etc [3, 6, 10, 15, 18, 19]. In many studies, different

techniques were used for cadmium analysis in water

and human blood samples such as, automated anodic

stripping voltammetry (ASV) technique with flow

injection system, atomic absorption spectrometry

(AAS), laser-induced breakdown spectrometry,

hollow cathode excitation coupled to vidicon

detection, atomic-fluorescence spectrophotometry,

neutron activation analysis (NAA), non-flame

atomic absorption spectrometry. [20-27]. Also,

other methods were reported for separation and

preconcentration of heavy metal in waters and

blood urine of neuropsychological and multiple

sclerosis patients [28-31]. Recently, the mesoporous

silica nanoparticles, silver nanoparticles, nano

carbon material, graphene and carbon nanotube

were widely used for separation heavy metals in

waters and human biological samples by different

analytical technology such as ultrasound-assisted

dispersive micro-solid-phase extraction (USA-

DμSPE) and ultrasound assisted-Ionic liquid trap-

micro solid phase extraction (USA-ILT-μSPE) [32,

33]. In this study, a new sorbent based on CAP-NPs

passed on MGR with IL was used for separation

of cadmium from blood and urine samples by

micro solid phase extraction(μ-SPE).All samples

analyzed by electro-thermal atomic absorption

spectrometer (ET-AAS).

2. Experimental

2.1. Apparatus and Reagents

Cadmium was determined with electro-thermal

atomic absorption spectrometer (ET-AAS Varian,

USA) which was equipped with graphite furnace

accessory (GFA). The current, wavelength and

spectral bandwidth of multi hollow cathode lamp

(MHCL) were tuned (wavelength 228.8 nm, slit

0.5 nm, lamp current 3.0 mA). All samples were

analyzed by auto-sampler injector of GFA. In

addition, the inductively coupled plasma mass

spectrometers (Varian ICP-MS, 810-MS, 820-MS

systems) with full PC control of all instrument

settings and compatible accessories. Varian ICP-

MS have gigahertz sensitivity (1000 Mc/s/mg/L)

and low background and interferences. The Varian

ICP-MS systems include a sample introduction

system and solid state 27 MHz RF generators.

Computer of Varian (ICP-MS) can be control of

plasma positioning, triple stage vacuum system,

all plasma gas flows, mass analyzer, and Discrete

Dynode Electron Multiplier (DDEM) detector. To

prepare the 1ppb multi-element test solution (1ppb),

pipette 1mL of the 500ppb into a 500mL volumetric

flask and dilute up to the mark using 1% HNO3,

other concentration from 0.05-0.9 ppb prepared

by dilution of DW (LOD= 2 ng L-1 cadmium).

The pH range of samples was determined by a

digital pH meter (M 744, Metrohm). The samples

Cadmium analysis by captopril-ionic liquid Mostafa Dehghani Mobarake et al

were shacked by a Vortex Mixer (Thermo USA).

All reagents purchased from Sigma Aldrich and

Merck Company from Germany. The nitric acid,

hydrochloric acid, polyoxyethylene octyl phenyl

ether, acetic acid, acetone and toluene (HNO3,

HCl, TX-100, CH3COOH, AC, C6H5 -CH3) were

purchased from Merck, Darmstadt, Germany. The

cadmium nitrate solution (500 mL, 1000 mg L−1,

99.98%) as cadmium(II) nitrate stock solution

(1% HNO3) was purchased from Merck(traceable

to SRM from NIST Cd(NO₃)₂ in HNO₃ 0.5 mol

L-1, CAS N: 119777 Germany). Standard solutions

(0.05, 0.1, 0.2, 0.5, 1 μg L-1 ) were prepared daily

by dilution of DW with 1% nitric acid. The pH

of the samples was adjusted with a phosphate

buffer (HPO4–H2PO4) for pH 5.5. Ultrapure water

(DW) was obtained from Millipore Continental

Water System (Bedford, USA). The CAP-NPs

(CAP, CASN: 62571-86-2, C₉H₁₅NO₃S) were

purchased from Sigma Aldrich (Germany). CAP

as an antihypertensive agent that competitively

inhibits angiotensin-converting enzyme (ACE;

IC50= 23-35 nM) act in human body. Also, ACP

acts as a reversible and competitive inhibitor of

LTA4 hydrolase (Fig. 1). Ionic liquids are made

up of charged species and imidazolium-based

ionic liquids have one of the nitrogen atoms in

the imidazolium ring in the cationic form. These

are generally synthesized by alkylation of an

N-alkylimidazole and further incorporation of

the desired anion by anion metathesis. 1-Butyl-

3-methylimidazolium hexafluorophosphate is

an imidazolium-based, hydrophobic, room

temperature ionic liquid (RTIL).1-Butyl-3-

methylimidazolium hexafluorophosphate{BMIM]

[PF6] is an ionic liquid employed in many

environmentally friendly analysis (CASN: 70956,

Sigma, Germany). 1-Methyl-3-(3-cyanopropyl)

imidazolium bis(trifluoromethylsulfonyl)amide

(CASAN: 38943 Sigma) as TSIL were purchased

from Sigma, Germany. Graphite rod, L 150 mm(15

cm), diam. 3 mm, low density(CASN: 496537,

99.995% trace metals). Micro graphite rod as 5

cm was used (micro rod of graphite, MGR, Sigma

Alderich)

2.2. Preparing of solid phase

First, 50 micro gram of CAP, 100 micro liter of

ionic liquid and 2 mL of acetone mixed with MGR

by shaking at 5 min (50 oC). After drying in oven

(120oC), washing with DW at 25oC for 10 times

and then drying for 10 min at 120 oC. The CAP

physically passed on MGR based on IL was used

as solid phase for extraction cadmium from blood

samples.

2.3. Extraction Procedure

By μ-SPE procedure, the CAP-IL-MGR was used

for separation and determination cadmium in

of blood/serum/urine samples by ET-AAS. The

procedure was developed as follows: 10 mL of blood

samples and standard solution containing 0.05-0.35

μg L−1 of cadmium was used for further analysis

after the pH adjusted up to 5.5 with phosphate

buffer solution. Then, the graphite rod - IL/CAP

was placed in real samples which were shaken for

5 min. Cd (II) ions were extracted from samples

by thiol group of CAP. Then, the rod was taking

out from samples and eluted with nitric acid (0.25

mL, 0.5 M) which was diluted with DW up to 0.5

mL. Finally, the obtained solution was determined

by ET-AAS. The proposed method followed by

MGR without CAP or IL at room temperature. The

concentration of cadmium in DW as a blank sample

was determined by μ-SPE method (Fig. 2).

3. Results and Discussion

3.1. Characterizations of CAP-NPs

The characterization of CAP nanomaterials

on MGR were achieved by X-ray diffraction

spectroscopy (XRD) (Fig. 3), scanning electron

microscopy (SEM) (Fig. 4), Fourier transform

Fig. 1. The structural of captopril nanoparticles(CAP-

NPs)

Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)

infrared spectroscopy (FTIR) (Fig. 5) and UV

spectrum analysis (UV-Vis) with absorption in

400 nm (Fig. 6). The X-ray diffraction (XRD) was

used to determine the CAP-NP structure. Due to

the XRD spectra of CAP-NPs, no change was seen

after coating on MGR (Fig. 2). In the CAP-NP, the

peaks at 2979 and 2877 cm-1 were assigned to the

asymmetric CH3 and CH2 stretching vibration, and

the peak at 2634 cm-1 was due to the symmetric

CH3 stretching mode. The peak at 2567 cm-1

corresponded to the SH stretching vibration. The

peaks at 1747 and 1593 cm-1 were assigned to

the C=O stretching vibration of carboxylic acid

and amide band, respectively. The peaks at 1471

and 1385 cm-1 were due to the asymmetric and

symmetric CH3 bending vibrations, respectively.

The peak at 1330 cm-1 was assigned to the OH

bending vibration. The peaks at 1228–1200 cm-1

also corresponded to the C-O and/or CN stretching

vibrations (Fig 4). The SEM and TEM of graphite

rod were showed in Figure 7(a) and 7(b) based

Fig. 3. The X-ray diffraction spectroscopy (XRD) of

CAP nanomaterials

Fig. 4. The scanning electron microscopy (SEM) of

CAP nanomaterials

Fig. 6. The UV spectrum analysis (UV-Vis) of CAP in

400 nm

Fig. 5. The Fourier transform infrared spectroscopy (FT-

IR) of CAP nanomaterials

Fig. 2. The schema of cadmium extraction based on

CAP-IL-MGR by μ-SPE procedure

Cadmium analysis by captopril-ionic liquid Mostafa Dehghani Mobarake et al

on nano lawyer of graphite (≈100 nm) which was

coated with CAP/IL.

3.2. Optimization of methodology

The CAP-IL-MGR as a solid phased was used for

separation and determination cadmium in of blood/

serum/urine samples by μ-SPE procedure. Blood

samples and standard solution containing 0.05-0.3

μg L−1 of cadmium was used at pH 5.5. The effects

of parameters were studied and optimized for 10

mL of samples by CAP/IL/MGR.

3.2.1. The effect of pH

The pH is an important factor for cadmium

extraction in blood/urine sample. By proposed

procedure, the formation of the cadmium–CAP

as chelate agent (HS group) was evaluated for

different pH range from 2 to 11 for 10 mL standard

solutions containing 0.05-0.3 μg L− 1 of Cd(II).

Obviously, the efficient extraction for Cd(II) were

achieved in the pH ranges of 5.0–6.0 by thiol group

of CAP which was passed on MGR by butyl-3-

methylimidazolium hexafluorophosphate [BMIM]

[PF6]. Therefore, pH of 5.5 was selected as the

optimum pH for cadmium extraction with CAP@

IL in real samples (Fig. 8). The results showed, the

cadmium extracted by IL@MGR up to 33% by

amino acids (Cys) in serum and blood samples and

lower extracted in urine up to 18%.

Fig. 7(a).The SEM of graphite rod - CAP/IL Fig. 7(b).The TEM of graphite rod - CAP/IL

Fig. 8. The effect of pH on extraction of cadmium based on CAP by μ-SPE

Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)

3.2.2. The effect of concentration of CAP

The optimizing of CAP concentration was

achieved by minimum reagent which was lead to

total complex formation with highest extraction

efficiency for cadmium. The effect of CAP

concentration on the recoveries of cadmium was

investigated using various amounts of CAP in the

range of 0.1–1 μmol L−1 for 0.35 μg L−1 of Cd(II)

at pH 5.5. By increasing of CAP concentration, the

extraction recoveries of cadmium ions gradually

increased and the total Cd(II) were extracted using

0.45 μmol L−1 of CAP. However, the extraction

efficiencies of Cd(II) were not increased more

than 0.45 μmol L−1 (Fig. 3). So, the 0.5 μmol L−1

of CAP were selected as optimum concentrations

(Fig. 9).

3.2.3. The effect of sample volume

Sample volume (SV) must be optimized for

preconcentration and separation of cadmium from

blood/urine/standard solutions. Under optimized

conditions, the effect of sample volume was

studied in the range of 1–20 mL containing 0.35

μg L−1 of Cd(II). The results showed, the cadmium

ions can be extracted quantitatively up to 14 mL of

the sample. At higher volumes, the recovery values

decreased. Also, in higher sample volumes (more

than 14 mL), the CAP/ILs phase was partially

solubilized in sample solution and lead to non-

reproducible results. So, the sample volume of 10

mL was selected for further experiments (Fig. 10).

3.2.4. The effect of extraction time (CAP/Il-MGR)

For high precision and accuracy of results, the

extraction time was optimized at pH=5.5. Under

optimized conditions, the effects of shaking time

on the recovery efficiency of cadmium were

studied for 1–10 minutes. Based on obtained

results, the cadmium ions were efficient extracted

and separated from blood and urine samples after 5

min of sonication.

3.2.5. The effect of back extraction of MGR

After extraction process of cadmium by the

proposed method, the MGR based on CAP/IL was

back extracted with different acid solutions. By

decreasing of pH, the cadmium–CAP complexes

lead to the dissociation of complexing bond and

released into the aqueous phase. In order to identify

the best eluent for back-extraction of Cd(II) from

the solid phase, 0.2-1.0 mL of various mineral

acids (HNO3, HCl and H2SO4) with different

concentrations, 0.1– 1.0 mol L−1, were tested. The

results show that HNO3 (0.25 mL, 0.5 M) provides

higher recovery efficiency compared to the other

acids (Fig.11).

Fig. 9. The effect of concentration of CAP on extraction of cadmium based on CAP by μ-SPE

Cadmium analysis by captopril-ionic liquid Mostafa Dehghani Mobarake et al

3.2.6. The Interference study

Matrix effects are a very problematic factor for

cadmium extraction based on CAP/IL/MGR in

blood samples and must be studied by different

cations and anions. Since, the thiol group in

CAP acted as good chelating agent for extraction

of cadmium and other transition metals, so, the

different concentration of transition metals was

used and examined for evaluation of μ-SPE By

procedure, the recoveries of 0.35 μg L−1 of Cd(II)

were studied in present of individual interferences

ions. The deviation of the recovery by more than

5%was considered as the interference criterion. The

results showed that many ions such as Co2+, Cu2+,

Zn2+and Pb2+ can be tolerated up to at least 0.6-1

mg L−1 when determining the Cd(II) ions based on

CAP/IL/MGR by ET-AAS. For concentrations of

1 mg L−1 of K+, Na+, Mg2+, CO3

2−and PO3

− 4 which

are usually found in human blood/serum samples,

any interference was seen by proposed procedure.

Moreover, Ni2+ and Hg2+ can be tolerated up to

at least 0.03 mg L−1 and 0.045 mg L−1 for Cd(II)

extraction by CAP.

Fig. 10. The effect of sample volume on extraction of cadmium based on CAP by μ-SPE

Fig. 11. The effect of inorganic acids on back extraction of cadmium from CAP/IL/MGR

Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)

3.3. Validation

Validity of the developed method was obtained by

using standard reference materials (SRM,) from

the national institute of standards and technology

(NIST, Gaithersburg, USA).The procedure based

on CAP-NPs passed on MGR by ionic liquid was

used for cadmium extraction in human blood and

urine samples by μ-SPE. The results showed a good

agreement with SRM (Table 1). Also, the accuracy

and reliability of the results were verified by

spiking of blood and urine samples (10 mL). High

efficient recovery between the added and measured

amounts of cadmium was obtained by CAP-NPs

(Table 2). Recovery and absorption capacity for

CAP-NPs were achieved more than 95 % and 136.7

mg g-1, respectively. In optimized conditions, the

efficiency of extraction with IL, MGR, and CAP/

IL/MGR were obtained 8.5%, 7.3% and more than

95%, respectively.

3.4. Comparing to published methods

Since 2010, the different techniques for extraction

and detemination cadmium in human biological

fluids have been published. Different methology

such as liquid–liquid microextraction (LLME),

micro solid phase extraction (μ-SPE), magnetic

solid phase extraction (MSPE), column solid phase

extraction(CSPE) have already used for extraction

and speciation cadmium in liquid phase [33-37].

The figures of merit of the μ-SPE method compared

to recently published methods for cadmium

determination in human samples (Table 3).

4. Conclusions

A new method for the separation and determination

of ultra-trace levels of cadmium in human blood,

serum, plasma and urine samples were developed

by CAP/IL/MGR sorbent. Cadmium was

preconcentraed based on nanoparticles of CAP

pure and determined by μ-SPE coupled with ET-

Table 1. Validation of cadmium results was performed by standard reference material (SRM) by μ-SPE

SEM ICP-MS (μg L−1)Added (μg L−1)Found by μ-SPE * (μg L−1) Recovery (%)

SRM a0.032 ± 0.005 ------- 0.031 ± 0.002 96.9

0.03 0.06 2 ± 0.003 103.3

SRM b0.211 ± 0.013 ------- 0.206 ± 0.013 97.6

0.1 0.303 ± 0.018 97.0

SRM C0.262 ± 0.038 ------- 0.255 ± 0.012 97.3

0.1 0.351 ± 0.019 96.0

Mean value ± standard deviation based on three replicate measurements

a Concentration Values for SRM 955c Caprine Blood, Level 1(0.032 ± 0.006)

b Concentration Values for SRM 955c Caprine Blood, Level 2 (2.140 ± 0.240, Dilution with DW,1:10)

C Concentration Values for SRM 955c Caprine Blood, Level 3 (5.201 ± 0.038, Dilution with DW,1: 20)

ICP-MS: Inductively Coupled Plasma Mass Spectrometer (ICP-MS)

Table 2. Evaluation of cadmium extraction based on CAP by μ-SPE method in human biological samples by spiking

of cadmium standard

Samples Added (ng L−1) Found * (ng L−1) Recovery (%)

Serum 68.76 ± 3.45 -------

50 117.53 97.5

Blood ------- 179.54± 8.32 -------

100 280.03± 15.11 100.5

Urine ------- 234.32± 12.24 -------

150 379.75± 18.36 96.9

Plasma ------- 148.66± 6.87 -------

150 291.82± 14.55 95.4

 Mean value ± standard deviation based on three replicate measurements

Cadmium analysis by captopril-ionic liquid Mostafa Dehghani Mobarake et al

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103.

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Table 3. Comparing of proposed method based on μ-SPE with other publisher works

Techniques preparation Matrixes *LOD *EF/PF *RSD (%) Ref.

a VAM-DLLME APDC-IL water 0.048 76.9 4.1 33

SPE-F-AAS b WMCNT-BCBATT biological 0.2 100 3.2 34

CSPE-F-AAS C sorbent of Am 15 water 0.23 20.0 3.0 35

DFIA-TS-FF-AAS E IIP Hair 0.024 165 5.0 36

SPE-F-AAS M-MWCNT Blood 0.04 120 1.2 37

F DLLME-ET-AAs G TOMAS-X100 Blood, Urine 0.005 10.4 2.3 38

μ-SPE-ET-AAS H CAP-IL-MGR Blood, Urine 0.002 19.7 2.4 This work

*Linear rang (LR, μg L−1); Detection limit (DL, μg L−1), the relative standard deviation (RSD%)

a Vortex-assisted modified dispersive liquid-liquid microextraction (VAM-DLLME)

b Multi wall carbon nanotube- benzyl-4-[-chlororbenzylidene amine]-4H-1,2,4-triazole-3-thiol (BCBATT) C Amberlyst

15 as sorbent

D Thermospray flame furnace atomic absorption spectrometry (FIA-TS-FF-AAS)

E Ion imprinted polymer (IIP)

F Dispersive liquid–liquid microextraction coupled by elecrothermal atomic absorption spectrometer

G Trioctylmethyl ammonium thiosalicylate(TOMAS, TSIL)

H Captopril nanoparticles - ionic liquid ([HMIM] [PF6]) paste on micro graphite rod

AAS. The developed method provides relatively

lower LOD, LOQ and RSD (< 2%, n=10) with

favorite enrichment factor (19.7) and recoveries

(more than 95 %). .As low cadmium concentration

in blood and serum samples (< 0.2 μg L−1), a good

linear range from 0.01 μg L-1 to 0.35 μg L-1 was

used for a 10 mL sample by μ-SPE . In optimized

conditions, the accurate / precise results with simple

sample treatment and high efficient extraction

were obtained with CAP/IL/MGR sorbent before

cadmium concentration determined by ET-AAS.

5. Acknowledgements

The authors wish to thank the Petroleum Industry

Health Organization (PIHO), The Ethical

Committee of Iranian Petroleum Industry Health

Research Institute approved the human sample

analysis by Lab. of IPIHRI (R.IPIHRI.PN.1397. 010)

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