Anal. Method Environ. Chem. J. 4 (1) (2021) 5-15

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

Separation and determination of cadmium in water samples

based on functionalized carbon nanotube by syringe ﬁlter

membrane-micro solid-phase extraction

Jamshid Rakhtshah ^a,*

^aDepartment of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran

A B S T R A C T

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

Received 19 Nov 2020

Revised form 25 Jan 2021

Accepted 22 Feb 2021

Asimple and fast separation of cadmium (Cd) based on functionalized

carbon nanotubes with 2,3-dimercapto-1-propanol (CNTs@DHSP)

was achieved in water samples before a determination by atom trap

ﬂame atomic absorption spectrometry (AT-FAAS). In this study,

Cd(II) ions were extracted by syringe ﬁlter membrane-micro solid

phase extraction procedure(SFM-μ-SPE). Firstly, 20 mg of the

CNTs@DHSP as solid-phase added to 20 mL of water sample in

a syringe, then dispersed for 3 min after adjusting pH up to 7 and

pass through SFM very slowly. After extraction, the Cd(II) ions

were back-extracted from SFM/CNTs@DHSP by 1.0 mL of eluent

in acidic pH. Finally, the cadmium concentration was measured by

AT-FAAS. Under the optimal conditions, the linear range (2–90 μg

L⁻¹), LOD (0.75 μg L⁻¹) and enrichment factor (19.6) were obtained

(RSD<1.5%). The adsorption capacity of Cd(II) with the CNTs@

DHSP was obtained about 152.6 mg g^-1. The method was validated

by certiﬁed reference materials (SRM, NIST) and ET-AAS in water

samples.

Available online 28 Mar 2021

------------------------

Keywords:

Cadmium,

Separation,

Water,

Functionalized carbon nanotubes,

Syringe ﬁlter membrane micro solid

phase extraction,

Atom trap ﬂame atomic absorption

spectrometry

gastrointestinal and respiratory tract system

1. Introduction

from food, water, air pollution and smoking. The

cadmium exposure causes to hepatic dysfunction,

the pulmonary edema, the testicular damage, the

osteoporosis and cancer in different organs such as,

breast, renal, lung and pancreas [3,4]. The Cd ions

absorb through the respiratory tract or the gastro-

intestinal tract and enters into the bloodstream via

erythrocytes and accumulated in the kidneys liver [5].

Cadmium ions excrete from the human body through

urine. The liver and kidneys are able to synthesize

metallothioneins (MT) which protect the cells from

cadmium toxicity through bonding to cadmium

(Cd- MT) [6]. Mitochondria play a crucial role in

the formation of ROS (reactive oxygen species) for

cadmium [7]. Moreover, the different methodologies

Cadmium (Cd) as a toxic non-essential metal

release from industrial activity to water, soil, food,

agricultural product and air, then, cadmium ions

cause to environmental and human health hazards.

Cadmium is naturally creating in the environment

matrixes from agricultural and chemical industrial

sources. The sources of cadmium have various

applications in different industry such as PVC

products in petrochemical industries, pigments

in color factories, and Ni-Cd batteries [1,2].

The cadmium enters to the human body through

*Corresponding Author: Jamshid Rakhtshah

Email: jamshid_rakhtshah@yahoo.com

https://doi.org/10.24200/amecj.v4.i01.132

Anal. Method Environ. Chem. J. 4 (1) (2021) 5-15

6

such as microbial fermentation based on TiO₂

nanoparticles have been used to remove cadmium

from waters efﬁciently [8,9]. The cytotoxic effects of

cadmium cause to apoptotic effect in human which

was reported by internationalAgency for research on

cancer (IARC) [10]. Itai itai disease or osteomalacia

is chronic cadmium poisoning was reported in Japan.

The cadmium intake to the human body is about 7 μg

Cd per week. This value cause to create the cadmium

concentration in renal and urine between 100-200 μg

g^-1and less than 0.5 μg g^-1creatinine, respectively.

Blood and urinary cadmium at 0.38 μg L^-1and

0.67 μg g^-1creatinine were associated with tubular

impairment. Urinary cadmium at 0.8 μg g^-1creatinine

was associated with glomerular impairment [11]. So,

the extraction and determination of Cd(II) in waters

is very important, due to the environment and human

health safety. Recently, various analytical techniques

can be used for cadmium extraction in different

water, foods and environmental samples. The

various methods such as ﬂame atomic absorption

spectrometry (AAS) [12], the optical microscopy

based on laser-induced photoluminescence (UV–

VIS-NIR) [13], the SrFe₁₂O₁₉@CTAB magnetic

nanoparticles with electrothermal atomic absorption

spectrometry (ET-AAS) [14-17], the colorimetric

sensor [18], the electrothermal vaporization coupled

with optical emission spectrometry with inductively

coupled plasma (ETV-ICP-OES) [19] and laser-

induced breakdown spectroscopy (LIBS) [20]

were used for cadmium determination in various

environmental samples. Due to the low concentration

of cadmium in water samples and difﬁculty matrixes

in wastewater samples, the pretreatment is required

before the determination of cadmium by instrumental

analysis. The different extraction methods such as,

the ultrasound-assisted liquid–liquid spray extraction

(USA-LLSE) [21], the solvent extraction [22], the

liquid–liquid extraction [23], the cloud point assisted

dispersive ionic liquid-liquid microextraction

[24] the dispersive solid-phase extraction (DSPE)

combined with ultrasound-assisted emulsiﬁcation

microextraction [25], solid-phase extraction

(SPE) [26, 27], the coagulating homogenous

dispersive micro solid-phase extraction exploiting

graphene oxide nanosheets (CHD-μSPE)[28] and

graphene oxide-packed micro-column solid-phase

extraction[29] were used before cadmium analysis in

water samples. Recently, the membrane micro solid-

phase extraction procedure (M-μ-SPE) was reported

as micro SPE (μ-SPE) for separation/determination

of cadmium in water samples. This method showed

several advantages, such as easy and fast extraction

of cadmium in water samples. The properties of

adsorbents have a main role for cadmium extraction

by the syringe ﬁlter membrane micro solid-phase

extraction procedure (SFM-μ-SPE). In this study, a

novel sorbent based on CNTs@DHSP was used for

extraction of Cd(II) in water and wastewater samples

by SFM-μ-SPE at pH of 7. The proposed method was

validated with CRM and spike samples in waters and

high recovery was obtained by AT-FAAS.

2. Experimental

2.1. Material and Methods

Atomtrapﬂameatomicabsorptionspectrophotometer

(GBC 932, AT-FAAS, Aus) was used for cadmium

determination in water and wastewater samples.

The atom trap accessory /air-acetylene controlled

by AVANTA software which was placed on the air-

acetylene burner. The cadmium determines in water

and wastewater samples with 1.0 mL of the sample

with LOD of 0.025 mg L^-1, the wavelength of 283.3

nm and 5 mA. The lower limit of quantitation

(LLOQ), ULOQ and linear range for AT-FAAS

was obtained 100 μg L⁻¹, 1800 μg L⁻¹and 100-

1800 μg L⁻¹, respectively. All water samples were

injected by an auto-sampler to the injector of AT-

FAAS for 1-1.5 min. The electrothermal atomic

absorption spectrophotometer (ET-AAS) was

used for the validation of water samples in ultra-

trace analysis of Cd(II). The Metrohm pH meter

was used for measuring pH in water samples (E-

744, Switzerland). The shacking of water samples

was used based on 250 rpm speeds by vortex

mixer (Thermo, USA). The standard solution of

cadmium (Cd²⁺) was purchased from Sigma Aldrich.

(Germany) with a concentration of 1000 mg L^-1in

1 % HNO₃. The various concentration of cadmium

was daily prepared by dilution of the standard Cd

Cadmium extraction by CNTs@DHSP

Jamshid Rakhtshah

7

solution with DW. Ultrapure water was purchased

from Millipore Company (USA) for the dilution

of water samples. 2,3-Dimercapto-1-propanol

(CASN:59-52-9, HOCH₂CH(SH)CH₂SH) was

prepared from Sigma Aldrich, Germany. The pH

was adjusted pH by 0.2 mol L^-1of sodium phosphate

buffer solution (Merck, Germany) for a pH of 7.0

(Na₂HPO₄/NaH₂PO₄). The analytical grade of

reagents such as HNO₃, HCl, acetone, and ethanol

were prepared from Merck, Germany. The syringe

Whatman ﬁlter membrane (SFM) with glass

microﬁber pre-ﬁlter (100 nm, Anotop ﬁlters, SN:

WHA68091112, D:10 mm, polypropylene housing

polypropylene membrane) was purchased from

Sigma Aldrich, Germany. Anotop syringe ﬁlters

contain the proprietary alumina and use for difﬁcult

separation samples.

mixture, drop by drop, at room temperature. After

sonicating for 15 min, the resulting mixture was

reﬂuxed at 60 °C under N₂atmosphere to remove

the produced HCl. In order to obtain the CNTs@Cl,

it was dried at 100 °C under vacuum. Then, 1 g of

CNTs@Cl and 1 mL of DMP were mixed in 60 mL

ethanol using an ultrasonic bath for 30 min. Then, a

few drops of triethylamine were added to the above

slurry, and the mixture was reﬂuxed at 60 °C for

three extra hours. The product was separated from

the reaction mixture by a PTFE membrane ﬁlter and

washed with ethanol three times and ﬁnally dried

under vacuum at 100 °C.

2.4. Extraction Procedure

By SFM-μ-SPE procedure, 20 mL of water and

standard samples (3 μg L⁻¹and 90 μg L⁻¹) were

used for the separation and determination of

cadmium ions at pH 7. Firstly, the CNTs@DHSP

added to water or cadmium standard solution

and shaked for 3 min at pH=7. Then, the water

sample was slowly passed through SFM with

glass microﬁber pre-ﬁlter and the solid-phase was

separated by ﬁltering (100 nm, polypropylene

housing polypropylene membrane). After shaking,

the Cd(II) ions were extracted by sulfur group of

CNTs@DHSP as coordination bond or dative bond

at pH from 6-8 (Cd²⁺→: SH @CNTs) and then the

Cd (II) ions on SFM/CNTs@DHSP back-extracted

by 0.5 mL of eluent (1.5 M, HNO₃) at pH 2. Finally,

the cadmium concentration in remained solution

was determined by AT-FAAS after dilution with

DW up to 1 mL (Fig.1). The procedure was used

for a blank solution without cadmium ten times.

The calibration curve for Cd in standards solutions

was prepared (3- 90 μg L⁻¹) and enrichment factor

(EF) was calculated. The analytical parameters

showed in Table 1. Validation of methodology

was achieved by CRM for cadmium samples

and ETAAS analysis. The recovery was obtained

for cadmium by equation 1. The C_pand C_fis the

primary and ﬁnal concentration of Cd(II), which

was determined by SFM-μ-SPE procedure coupled

to AT-FAAS (n=10, Eq. 1).

2.2. Human sample preparation

The glass analysis was washed with a HNO₃solution

(1 M) for at least 12 h and rinsed 10 times with DW.

The cadmium concentrations in water and wastewater

have a low concentrations less than 50 μg L^-1and low

contamination for sampling and determination caused

to low accuracy of results. By procedure, 20 mL of

the water samples were prepared from well water,

drinking water and wastewater factories from Iran.

Clean syringes were prepared for sample treatment.

The water is prepared and stored by standard method

for sampling from water by adding nitric acid to waters.

2.3. Synthesis of CNTs@DHSP adsorbent

First, the CNTs@COOH was prepared according to

the acid oxidation method reported in the literature

[30]. In the ﬁnal step, 1 g of CNTs@COOH was

added in 50 mL of methanol and maintained

under ultrasonic conditions for 15 min. Sodium

borohydride was also simultaneously added to the

solution. Then, the mixture was stirred at room

temperature for 3 h. Then, the product was washed

with methanol three times and dried under vacuum.

Typically, CNTs@OH (0.5 g) and dry xylene (40

mL) were sonicated for 15 minutes in a 100 mL

round-bottomed ﬂask. 3 mL of (3-chloropropyl)

trimethoxysilane (CPTMS) was added to the above

Re (%) = (C_p-C_f)/C_p×100

(Eq.1)

Anal. Method Environ. Chem. J. 4 (1) (2021) 5-15

8

Table 1. The analytical features for determination cadmium by SFM-μ-SPE procedure

Features

Working pH

value

6-8

Amount of CNTs@DHSP (mg)

Sample volume of water (mL)

20.0

20 .0

Volume of sample injection (mL)

1.0

Linear range for water (μg L^-1)

working range for water (μg L^-1)

Mean RSD %, n=10

3.0-90

3.0-170

1.5

LOD (μg L^-1)

0.75

Enrichment factor for water

Volume and concentration of HNO₃

Shaking time

19.6

1 mL, 1.5 M

3.0 min

R²= 0.9998

Correlation coefﬁcient

Fig. 1. Cadmium extraction in water sample based on CNTs@DHSP by SFM-μ-SPE procedure

functionalized CNTs were functionalized by

(3-chloropropyl) trimethoxysilane (CPTMS) to

provide chloroalkylsilane. Finally, thiol derivative

as a DHSP was covalently immobilized on CNTs.

Finally, SH group of DHSP on the surface of CNTs

can be complexed with cadmium ions in a water

solution (Fig.2).

3. Results and discussion

3.1. Extraction Mechanism

The carboxylic acid-functionalized CNTs were

synthesized by using the acid oxidation method.

Then, for the generation of OH groups on surface

CNT, these materials were treated with sodium

borohydride in methanol. Afterward, hydroxyl-

Cadmium extraction by CNTs@DHSP

Jamshid Rakhtshah

9

Fig. 2. The extraction mechanism of cadmium by CNTs@DHSP

Fig.3a. SEM image of CNTs@DHSP

Fig.3b. TEM image of CNTs@DHSP

3.2. SEM and TEM analysis

3.3. Optimization of cadmium extraction SFM-

The nanotubes of CNTs syntheses in University

of Tabriz (Iran) and used for the synthesis of

μ-SPE procedure

The SFM-μ-SPE procedure based on novel CNTs@

DHSP was optimized for cadmium extraction in

water samples. So, different parameters such as

pH, CNTs@DHSP Mass, eluent, sample volume

and sonication time were studied.

2,3-dimercapto-1-propanol

immobilized

on

CNTs (CNTs@DHSP). The Scanning Electron

Microscopy (SEM) and Transmission Electron

Microscopy (TEM) of CNTs@DHSP showed low

nanoparticles size between 40-100 nm which was

shown in Figures 3a and 3b.

Anal. Method Environ. Chem. J. 4 (1) (2021) 5-15

10

3.3.1.The effect of pH

3.3.2. Effect of CNTs@DHSP mass

The effect of various pH was studied from 2 to

10 for Cd(II) extraction in water samples. The

results showed the CNTs@DHSP can be removed

cadmium ions from water samples at pH between

6 to 8. Moreover, the efﬁcient extraction was

achieved for cadmium ions at pH=7 (> 95%) and

the recoveries reduced at 6>pH and pH>8.5. So, the

pH of 7.0 was used as optimum pH for cadmium

extraction in waters for further works (Fig. 4).

The mechanism of cadmium extraction depended

on the coordination bond or dative covalent bond

of the thiol group in CNTs@DHSP adsorbent

(Cd→:SH). The positively charge of Cd²⁺adsorbed

on the surface of adsorbent with negative charge at

optimized pH. At low pH (pH< pH_PZC), the surface

of CNTs@DHSP has a positive charge. Therefore,

low recovery is related to the electrostatic repulsion

between Cd²⁺and positive charge of CNTs@DHSP.

In addition, at a pH of 7, the surface of CNTs@

DHSP have negatively charged and absorbed Cd²⁺.

Also, in the pH>8.5, the Cd ions participated as OH

group and the recovery was decreased.

The efﬁcient extraction was obtained by optimizing

of CNTs@DHSP mass in pH=7. Therefore,

the various of CNTs@DHSP mass was studied

between 5-50 mg for Cd(II) extraction by SFM-

μ-SPE procedure. The results showed us, a high

recovery of more than 95% was achieved for 18

mg of CNTs@DHSP in water samples. So, 20 mg

of CNTs@DHSP as optimum adsorbent mass was

used for the experimental run. (Fig. 5). Based on

Figure 6, The higher amount of CNTs@DHSP had

no effect on cadmium recovery.

3.3.3. Effect of eluent and sample volume on

cadmium extraction

The volume and concentration of eluent for back

extraction cadmium ions from SFM/CNTs@

DHSP adsorbent were optimized at pH=7. Acidic

pH dissociated thiol binding to cadmium and

caused to release of free cadmium ions into the

eluent phase. The different acid solution such as

HCl, HNO₃, NaOH and H₂SO₄, was selected for

back-extraction of cadmium from SFM/CNTs@

Fig. 4. The effect of pH on cadmium extraction based

on CNTs@DHSP by SFM-μ-SPEprocedure

Cadmium extraction by CNTs@DHSP

Jamshid Rakhtshah

11

Fig. 5. The effect of CNTs@DHSP amount on cadmium extraction

by SFM-μ-SPE procedure

DHSP adsorbent. The results showed that 1.5 mol

L^-1HNO₃was quantitatively back-extracted the

cadmium from SFM/CNTs@DHSP adsorbent. The

sample volume between 1-100 mL for cadmium

extraction was studied in water samples by SFM-

μ-SPE procedure. For optimization, the cadmium

concentration ranges (3-90 μg L^-1) based on 20 mg

of CNTs@DHSP adsorbent were examined by the

proposed procedure. The results showed us the high

recoveries were achieved 25 mL of water samples

at pH=7. Therefore, 20 mL of water was used as the

optimal value for further study.

The absorption capacities of cadmium for CNTs@

DHSP and CNTs adsorbents were evaluated in

optimized conditions. First, 20 mg of CNTs@

DHSP or CNTs adsorbents added to 20 mL of water

sample (standards cadmium solution: 200 mg L^-1)

at pH 7. After sonication for 20 min, the cadmium

extracted on the CNTs@DHSP or CNTs adsorbents

at optimizing pH. The cadmium concentration in

the liquid phase is directly determined as the ﬁnal

cadmium concentration after adsorption processes.

The results showed the adsorption capacity for the

CNTs@DHSP or CNTs adsorbents was obtained

152.6 mg g^-1and 19.7 mg g^-1, respectively.

3.3.4. Effect of sonication time and adsorption

capacity

3.3.5. Interference of coexisting ions

Theeffectofinterferenceionsoncadmiumextraction

based on CNTs@DHSP adsorbent in water samples

was studied by SFM-μ-SPE procedure. The various

interfering ions were added to 20 mL of cadmium

solution (ULOQ: 90 μg L^-1) at pH 7. Based on

results the most of the probable concomitant ions

have no effect on the extraction recovery of Cd(II)

ions in optimized conditions (Table 2).

The extraction time depended on the dispersion

of nanoparticles CNTs@DHSP adsorbent in the

water samples and caused to increase interaction

between HS with Cd(II) at pH=7. The effect of

sonication time was studied from 0.5 to 5 min. It

was observed that the sonication of 3.0 min had

favorite extraction for cadmium in water samples.

Anal. Method Environ. Chem. J. 4 (1) (2021) 5-15

12

Table 2. The effect of interferences ions on cadmium extraction in water samples

by SFM-μ-SPE procedure

Mean ratio (C_I/C _Cd(II)

Cd(II)

)

Recovery (%)

Cd(II)

Interfering Ions (I)

Al³⁺, V³⁺

600

900

96.8

08.0

99.2

Zn²⁺, Cu²⁺

I^-, Br^-, F^-, Cl^-

1200

Na⁺, K⁺

Ca²⁺, Mg²⁺

1000

900

98.4

97.7

CO₃^2-, PO₄^3-

1000

97.2

Co²⁺, Mn²⁺, Sn²⁺

Ni²⁺

NH₄⁺, NO3^-

350

150

800

98.3

96.7

98.5

Hg²⁺

100

97.4

3.3.6. Real samples analysis

procedure could be efﬁciently extracted/determined

cadmium in water samples (Table 3). Due to results,

thehighrecoveryforextractioncadmiuminwaterand

wastewater samples was achieved by nanoparticles

of CNTs@DHSP. Moreover, the certiﬁed reference

materials (NIST; CRM) were used for validating

results by the SFM-μ-SPE procedure (Table 4). Also,

the results were validated by ET-AAS analysis which

was compared to SFM-μ-SPE/AT-FAAS (Table 5).

The separation and determination of cadmium in

water samples was done based on CNTs@DHSP

adsorbent by the SFM-μ-SPE procedure. The results

showed us, the cadmium was efﬁciently extracted by

the thiol group of CNTs@DHSP adsorbent in water

samples at pH=7. By spiking water samples, the

accuracy of the results was satisfactorily validated

at optimized pH and conﬁrmed that the SFM-μ-SPE

Table 3. Validation of SFM-μ-SPE/AT-AAS procedure for Cd(II) determination in waters

by spiking of real samples

Sample*

Water A

Added(μg L^-1)

^*Found (μg L^-1)

Recovery (%)

---

4.0

---

4.23 ± 0.18

8.14 ± 0.31

2.03 ± 0.09

3.98 ± 0.21

ND

---

97.8

---

Water B

2.0

---

2.0

---

97.5

---

96.5

---

Water C

1.93 ± 0.08

50.75 ± 1.23

Wastewater A

40

---

40

---

30

88.83 ± 2.64

48.32 ± 1.87

89.56 ± 3.45

29.56 ± 1.34

57.95 ± 2.08

95.2

---

Wastewater B

Wastewater C

103.1

---

94.6

*Mean of three determinations of samples ± conﬁdence interval (P = 0.95, n =5)

WaterA: Varamin River; Water B: Karaj River; Water C: drinking water Tehran; WastewaterA: Paint Factory of Karaj; Wastewater

B: Petrochemical waste; Wastewater C: Chemical Factory in Industrial Varamin Co.

Cadmium extraction by CNTs@DHSP

Jamshid Rakhtshah

13

Table 4. Validation of SFM-μ-SPE procedure for cadmium determination

by certiﬁed reference materials in waters (CRM, NIST)

Sample

conc.( μg L^-1)

Added

Found^*( μg L^-1)

Recovery (%)

SRM 1643f

5.89 ± 0.13

-----

5.0

5.82 ± 0.16

10.79 ± 0.25

48.77  1.42

87.64  2.61

-----

99.4

-----

97.2

SRM 3108

50.10  1.1

-----

40

^*Mean of three determinations of samples ± conﬁdence interval (P = 0.95, n =10)

SRM 3108: Certiﬁed Cadmium Mass Fraction: 10.007 mg g^-1± 0.027 mg g^-1dissolved in 1 L DW (C=10 mg L^-1),

make by dilution DW up to 0.05 mg L^-1.

Table 5. Comparing of SFM-μ-SPE procedure with ET-AAS for cadmium determination in water samples

Sample

Added ( μg L^-1)

ET-AAS* ( μg L^-1)

4.18 ± 0.17

-----

AT-FAAS^*( μg L^-1)

4.06 ± 0.13

7.98 ± 0.24

2.18 ± 0.08

4.09± 0.16

^aND

Recovery (%)

-----

Water A

-----

4.0

98.0

Water B

-----

2.0

2.12 ± 0.11

-----

95.5

Water C

-----

2.0

0.25 ± 0.02

-----

1.97 ± 0.09

5.94 ± 0.18

11.03± 0.34

98.5

Well water

-----

5.0

6.12 ± 0.28

-----

101.8

^*Mean of three determinations of samples ± conﬁdence interval (P = 0.95, n =10)

^aND: Not Detected

4. Conclusions

6. References

A novel CNTs@DHSP nanostructure was used for

cadmiumextraction/separation/determinationinwater

samples by the SFM-μ-SPE method coupled with

AT-FAAS. By the proposed procedure, the efﬁcient/

easy/fast extraction for cadmium was obtained in a

short time at pH=7. The CNTs@DHSP nanostructure

has excellent recovery for Cd(II) extraction without

any chelating ligands. The procedure had many

advantages such as reusability of adsorbent, fast/easy

pretreatment and a wide linear range for determination

cadmium in waters. Therefore, the CNTs@DHSP

nanostructure can be used as the favorite methodology

for the determination and separation of cadmium in

water samples by AT-FAAS.

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