Aluminum separation from drinking water and serum

samples based on djenkolic acid immobilized on the multi

walled carbon nanotubes by ultrasound-assisted dispersive

micro solid phase extraction

Farnaz Hosseini*, a and Sara Davari b

a Islamic Azad University, Tehran Medical Branch, Iran

b Islamic Azad University, Tehran Medical Branch, Iran

ABSTRACT

A new method for aluminum extraction from drinking water

and human serum samples was used by djenkolic acid (DJKA)

immobilized on multi walled carbon nanotubes (MWCNTs-DJKA).

By procedure, the mixture of 25 mg of MWCNTs-DJKA sorbent

and hydrophobic ionic liquid ([OMIM][PF6]) were dispersed with

ultrasonic bath in 10 mL of drinking water and serum samples for 10

min at pH=5. The aluminum ions were extracted based on MWCNTs-

DJKA sorbent in liquid phase by ultrasound-assisted dispersive micro

solid phase extraction (USA-D-μ-SPE). After centrifuging, the Al

(III) was separated from liquid phase by ionic liquid phase in bottom

of centrifuge PVC tube. Finally, the Al (III) were back-extracted

from sorbent/IL in acidic pH and measured by electrothermal atomic

absorption spectrometry (ET-AAS). In optimized study, LOD,

LOQ, the linear range, the working range and the enrichment factor

were obtained 0.1 µg L−1, 0.3 µg L−1, 0.3-12.8 µg L−1, 0.3-30.7 µg

L−1 and 9.92, respectively (RSD< 5%). The adsorption capacity of

the MWCNTs-DJKA sorbent was obtained in batch system. Based

on proposed procedure, the mean concentrations of aluminum in

drinking waters and serum samples were lower than world health

organization (WHO) and American conference of governmental

industrial hygienists (ACGIH) references. The method was validated

by spiking samples and standard reference materials (SRM) in water

and human biological samples.

Keywords:

Aluminum,

Poly methyl ether thiol sorbent,

Dispersive micro solid phase extraction,

Waters,

Human serum,

Electrothermal atomic absorption

spectrometry

Anal. Method Environ. Chem. J. 3 (2) (2020) 82-91

ARTICLE INFO:

Received 2 Mar 2020

Revised form 30 Apr 2020

Accepted 21 May 2020

Available online 29 Jun 2020

Research Article, Issue 2

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

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

1. Introduction

Aluminum used in different products such as

pharmaceuticals (Al-Mg/S), cover or additives for

foods, plates, cars and airplanes. The aluminium

compounds have solid forms with high melting points

and solubility in water in low pH. The aluminium

cation (Al3+) has a strong afnity to hydroxide form

[Al (OH)3] as precipitation. Aluminium production”

has been classied as carcinogenic to humans by

the International Agency for Research on Cancer

(IARC). Aluminium in the diet has ranges between

0.1 to 0.3% based on aluminium intake and urinary

elimination. Over dose of aluminum caused to

Alzheimer’s disease (AD). Aluminium is the most

* Corresponding Author: Farnaz Hosseini

Email: hfarnaz.1990@gmail.com

https://doi.org/10.24200/amecj.v3.i02.105

Aluminum extraction by MWCNTs-DJKA Farnaz Hosseini et al

abundant metal and the third most abundant element

in the Earth’s crust. This metal separated from its

ores by industrial scale and caused to change from

decorative metal to the most widely used metal in

different industries [1]. WHO reported that aluminum

salts can be absorbed by the gut and concentrated in

various human tissues including bone, parathyroid,

and brain. Aluminum concentrations in brain tissue

should be lower than 2 μg g-1. The daily dietary intake

of aluminum (510 mg) is completely eliminated.

On the other hand, the pervious works showed

that the high aluminum intake may be harmful

to some patients with bone or renal diseases [2].

Also, the aluminum can be detected in brain tissues

of patients with Alzheimer’s disease [3] and the

pulmonary brosis have been evident under high-

dose aluminum exposure [4]. The neurotoxicity

of aluminium has been demonstrated in humans,

animal models and in tissue and cell culture. The

neurotoxicity of aluminum is indisputable and it is

difcult to understand the mechanism of neurotoxin

in human body [5].Aluminium toxicity created

from the interaction between aluminum and plasma

membrane and in humans Mg2+ and Fe3+ are replaced

by Al3+, which causes many disturbances associated

with intercellular interaction [6]. Workers are

exposed to various occupational hazardous factors

such as fumes and gases, mineral dusts, and VOCs.

Workers in aluminum factory were shown the

respiratory symptoms, phlegm, dyspnea, wheezing

and chest tightness [7].Also, it has been shown

that Bauxite mining causes respiratory and skin

problems, in addition to other injuries consistent

with mining and heavy industries. Workers

in alumina reneries have symptoms include

osteosclerosis, sinus trouble, chest pains, coughs,

thyroid disorders, anemia, dizziness, weakness and

nausea. As hazards of aluminium in environment and

humans, determination and separation aluminum in

human body and waters is very necessary. Many

analytical techniques was used for determination of

aluminum in different matrix such as ame atomic

absorption spectrometry (F-AAS) [9], stripping

Voltammetry (SV) [10], inductively coupled

plasma-atomic emission spectrometry (ICP-AES)

[11], High performance liquid chromatography/

inductively coupled plasma mass spectrometry

(HPLC/ICPMS) [12,13], electrothermal atomic

absorption spectrometry (ETAAS) [14] and

inductively coupled plasma mass spectrometry

(ICP-MS) [15]. Also, sample preparation was

needed for separating of contaminations from water

and biological samples. For this purpose, the vary

preconcentration/separation techniques such as

liquid–liquid extraction (LLE), dispersive liquid–

liquid microextraction (DLLME) [16, 17], and solid

phase extraction (SPE) [18] was applied. Recently,

the SPE methods were used as a suitable technique

for extraction aluminum as compared to others. The

SPE have some advantages including simplicity,

lower cost, higher enrichment factor, less lower

LOD, and the ability to combine with different

detection techniques such as ICP-MS [19, 20]. The

aim of this study is to develop a novel technique

based on MWCNTs-DJKA sorbent for separation

and determination of aluminum from drinking

water and human serum samples by USA-D-μ-SPE

procedure coupled to ET-AAS.

2. Experimental

2.1. Instrumental

The spectra GBC atomic absorption spectrometer

(AAS, Plus 932, Australia) using a electrothermal

module (ET-AAS) was used for determination

aluminum in different samples. The parameters of

alminum of were adjusted by recommended of the

manufacturer. A multi cathode lamp for Al (MCL)

with the current lamp (6 mA), the wavelength

(396.2 nm) and spectral bandwidth (0.5 nm)

was applied. All results were performed by auto

injection of samples (1-100μL) and ANANTA

software. The pH in water and serum samples

were determined and adjusted by a pH-meter of

Metrohm (744, Switzerland) which was with a

glassy electrode. The samples were separated using

a centrifuge accessory (Eppendorf, 5702 Series

Centrifuge, 022629905, 4,400rpm) with rotor (A-4-

38) and round bucket(4 × 85 mL), rotary knobs. An

ultrasonic bath (100DE, China) with temperature

control was used in this study.

84 Anal. Method Environ. Chem. J. 3 (2) (2020) 82-91

2.2. Material and Reagents

The reagents such as acids, bases and organic and

inorganic solvents were purchased from Merck

Company (Germany, ultra-trace grade). MWCNTs

(particle size <100 μm) was prepared from RIPI,

Iran. DL-djenkolic acid (C7H14N2O4S2, DJKA,

CAS N.: 28052-93-9) was purchased fron sigma

Aldrich, Germany. 1-methyl-3-octylimidazolium

hexauorophosphate ([OMIM] PF6]), CAS N:

304680-36-2, Purity > 99.0 ). Standard stock

solutions (1000 ppm) of Al (III) purchased from

Merck, Darmstadt, Germany. Deionized water

(DW) prepared from Milli-Q plus water purication

system (Millipore, Bedford, MA, USA). The all

solutions of procedure were daily prepared by

diluting of standard solutions with DW. The eight

point of calibration curve for aluminum were

prepared daily by diluting the stock solutions of

alminum ions with DW prior to analysis. The pH

adjustments were made using appropriate buffer

solutions including ammonium acetate (CH3COOH/

CHCOONH4, 0.2 Mol) for pH 4-6 in this study.

2.3. Sampling

All glasses and PVC tubes were cleaned with a

mixture of 0.1 M of HNO3/H2SO4 solution for

12 h and washed for 10 times with DW before

using. As trace concentrations of Al in serum and

drinking water, even low contamination at any

step of sample storage, preparation, and analysis

can be effected on the accuracy of the results.

Human serum samples collected into 2 mL of

Eppendorf tube tubes and kept at -20OC. Serum

and wastewater samples were collected from

aluminum factories, Iran. The water prepared and

stored by standard method for sampling from water

by adding HNO3 (2%) to waters. In this study, the

world medical association declaration of Helsinki

(WMADH) based on guiding physicians in human

body research was considered.

2.4. Characterization

The Brunauer-Emmett-Teller (BET) method was

used for studying the microstructure (surface area

and pore size) of nanostructure. The surface area

and porosity of the MWCNTs and MWCNTs-

DJKA, before and after heat treatment in 350OC

were almost similar. The structure of MWCNTs

and MWCNTs-DJKA including length, diameter

and surface area were provided in Table 1. In this

study, the surface area of MWCNTs was found 375

m2 g-1, which was similar to previous literature for

MWCNT. The low specic surface area in CNTs

depended on the large diameters and many walls.

The surface area of MWCNTs-DJKA (345 m2 g-1)

is little lower than simple MWCNT (375 m2 g-1)

because of MWCNTs functionalized with DJKA.

2.5. Procedure of aluminum extraction

By procedure, the aluminum ions were extracted

from drinking water and human serum samples

by MWCNTs-DJKA. In this work, the mixture

of 25 mg of MWCNTs-DJKA adsorbent and

[OMIM][PF6] were added to 10 mL of samples

and dispersed with ultrasonic bath for 10 min at

pH=5. The aluminum ions were extracted based

on MWCNTs-DJKA sorbent by ultrasound-

assisted dispersive micro solid phase extraction

(USA-D-μ-SPE). After centrifuging at 4000 rpm,

the Al (III) ions were separated from liquid phase

by hydrophobic ionic liquid phase in bottom of

centrifuge PVC tube. Finally, the Al (III) were

back-extracted from sorbent/IL with 0.5 mL of

HNO3 (0.1 M) and measured by ET-AAS after

dilution up to 1 mL with DW (Fig.1).

3. Results and Discussions

3.1. Synthesis of MWCNT

High-purity MWCNTs were synthesized by use of

camphor, an environment-friendly hydrocarbon as

a carbon source using chemical vapor deposition

Table 1. Comparind of the structure of MWCNTs and MWCNTs-DJKA

Carbon Nano Structure Diameter (nm) Length (um) Surface Area (m2/gr)

MWCNT 14-30 11-24 375

MWCNTs-DJKA 15-38 13-30 345

Aluminum extraction by MWCNTs-DJKA Farnaz Hosseini et al

(CVD) method on Co-Mo/MgO Nano-catalysts.

The Nano-catalyst synthesized by sol-gel method.

MWCNTs growth at temperatures of about

900-1000 oC in 45-60 minutes was conducted.

Concentration of active metals was 5-10%. The

Nano-catalyst (Co-Mo/MgO) was prepared by our

special sol-gel method (Sayes et al., 2006, Rashidi

et al., 2007). The composition of Co: Mo: Mgo for

MWCNTs was 2.5:2.5:95 molar ratio. In chemical

vapor deposition method, generally a precursor

gas as a carbon source enters the furnace. In this

study, the used experimental setup for CNTs

production consisted of a quartz tube reactor with

a length of 150 and 7 cm in diameter. It was heated

in a resistive furnace in the temperature range

from 900 to 1000 °C and at ambient pressure. The

camphor was used as the carbon precursor and

placed in the early part of the reactor and copper

Nano-catalyst was placed in the middle of the

reactor. The reactor was then put in a three thermal

zone furnace, the rst part for the evaporation of

camphor, Part II for the reaction zone and Part III

for cooling of the exhaust vapors. Before using

MWCNT as adsorbent, purication process and

meshing were performed.

3.2. Synthesis of Djenkolic on MWCNTs

The immobilization of 3,3′-(Methylenedithio)

dialanine (djenkolic acid, DJKA) on multi-wall

carbon nanotubes was obtained. The pure MWCNTs

(0.5 g) were mixed with H2SO4 and HNO3 solutions

and chaked with 300 rms for 2 h. The MWCNTs were

oxidized based on carboxyl groups (MWCNTs-

COOH). Then, the MWCNTs-COOH were washed

with DW many times before it ltered with

Watman lter (0.2 nm) based on vacuum accessory.

Them, the carboxyl groups on MWCNTs (COOH)

convert to hydroxil group (OH) by reducing agent

and washed and dried before using. The 0.5 g of

MWCNTs-OH were dispersed in 10 mL of toluene

and 1 mL of 3-(trimethoxysilyl)propyl chloride

added drop by drop very quickly. The chloro silica

on MWCNTs prepared by reuxing, washing and

driing at 70 °C. Finally, the cholor functionized on

MWCNTs was used by djenkolic acid in ethanolic

solution which was shaked with 20 micro liter of

N,N-diethylethanamine for 20 min before reuxed

at 70 °C for 2 h. Finally the product of MWCNTs-

DJKA was synteszed. The sulfur groups of this

molecule act as chelation sites to which divalent

metal ions coordinate. In addition to these groups,

the formation of a stable ring with metal ions is

a factor of increasing efciency on the trapping

process in the variable conditions (Fig. 2).

3.3. FTIR Analysis

The appearance of a broad peak in the range

2500–3600 cm−1 in the FTIR spectra of these

compounds is due to the characteristic O–H and

NH stretching vibration of enolic, carboxylic, and

Fig. 1. Procedure of aluminum extraction based on MWCNTs-DJKA by USA-D-μ-SPE

86 Anal. Method Environ. Chem. J. 3 (2) (2020) 82-91

Amine functionalities. As Figure 3, The absorption

bands at 3420, 1718, 1623, and 1060 cm−1 shown in

the spectra of MWCNT and MWCNTs-DJKA are

ascribed to the stretching bands ν(O–H), ν(C=O),

ν(C=C), and ν(C–O) respectively. Moreover, the

peak at 1410 cm−1 may be attributed to tertiary

OH groups [53,54]. Also, the characteristic bands

observed at around 1062 and 1169–1218 cm−1 in the

spectra of the MWCNTs-DJKA and GO correspond

to the vibration bands of ν(S=O) derived from

SO3H groups. The presence of SO3 group is also

conrmed by the presence of the peak at 1221 cm−1.

Fig. 2. Synthesis of Djenkolic on MWCNTs

Fig. 3. FTIR spectra of a) MWCNT and b) MWCNTs-DJKA

Aluminum extraction by MWCNTs-DJKA Farnaz Hosseini et al

3.4. SEM and XRD Analysis

After synthesis, the SEM images of MWCNTs and

MWCNTs-DJKA were obtained which was shown

in Figure 4a and 4b. Nitrogen adsorption The

X-ray diffraction (XRD) spectrum of MWCNTs

and MWCNTs-DJKA was shown in Figure 5. The

XRD of MWCNTs-DJKA is similar to MWCNTs

and the crystallinity /morphology of MWCNTs

were preserved during synthesis of MWCNTs-

DJKA. The MWCNTs-DJKA showed typical peak

of (002), (110), and (400) at 2θ = 26.5, 42.4, and

52.7°, respectively.

3.5. Optimization of pH

The main factor for extraction aluminum from

serum and water samples is pH. So, the effect

of different pH from 2 to 10 was investigated by

USA-D-μ-SPE procedure. The results showed that

the MWCNTs-DJKA could be simply extracted

alminum in a pH of 4-6. Therefore, the efcient

extraction for Al(III) were achieved more than

97% at optimized pH and the recoveries were

decreased at pH more than 6 and less than 4. So,

pH=5 was used for further works in this study

(Fig. 6). The results showed that, aluminum can

Fig. 4. SEM of images of a) MWCNTs and b) MWCNTs-DJKA

Fig. 5. The X-ray diffraction (XRD) of MWCNTs and MWCNTs-DJKA

88 Anal. Method Environ. Chem. J. 3 (2) (2020) 82-91

be physically extracted by MWCNTs at pH=3

up to 34%. The mechanism of extraction

was carried out based on the coordination

of covalent bond between positively charged

of Al3+ and sulfur of DJKA which is highly

dependent on pH.

3.6. The effect of Ionic liquids and sonication

time

The different hydrophobic ionic liquids such

as [OMIM][PF6], [HMIM][PF6] and [BMIM]

[PF6] were used for separation of MWCNTs and

MWCNTs-DJKA from samples. The amounts of

ILs on the separation of MWCNTs and MWCNTs-

DJKA sorbents were tested between 0.01-0.2 g in

Al concentration from 0.3 µg L−1 as LLOQ and

12.8 µg L−1 as ULOQ. The results showed the the

best recovery was obtained by 0.1 g

of [OMIM][PF6]. Therefore, 0.12 g of

[OMIM][PF6] was used as optimum IL

for separation of aluminum in water

and serum samples.

3.7. Optimazation of amount of

MWCNTs-DJKA sorbent

For optimization of extraction,

the amount of MWCNTs and

MWCNTs-DJKA was studied

at pH=5. For this purpose,

the amounts of MWCNTs and

MWCNTs-DJKA between 1─40

mg were evaluated for Al(III)

extraction by the USA-D-μ-SPE

procedure. By results, the high

recoveries in water and serum

samples were achieved from

22 mg of MWCNTs-DJKA by

proposed procedure. So, 25 mg

of MWCNTs-DJKA was selected

as optimum amount of sorbent

(Fig. 7). The higher amount of

MWCNTs-DJKA had no effect on

the extraction recovery for Al(III)

in water samples.

3.8. The effect of elution and sample volume

The volume/ concentration of elution for back

extraction Al ions from MWCNTs-DJKA

were studied at pH of 5. So, the different

solutions such as HCl, HNO3, H2SO4 and

NaOH with different volume (0.2-1.0 mL)

and concentration (0.1-0.5 M) was used

for back extraction Al(III) from sorbents

by USA-D-μ-SPE procedure. The results

showed that 0.2 mol L-1 HNO3(0.5 mL) was

quantitatively back-extracted aluminum

from MWCNTs-DJKA.The sample volume

based on MWCNTs-DJKA was evaluated for

aluminum extraction between 1-20 mL serum

and water samples in ranges (0.3-12.8 µg L-1).

The results showed us the efficient extraction

were obtained for 10 mL of samples. By

Fig. 6. The effect of pH on aluminum extraction by MWCNTs and

MWCNTs-DJKA

Fig. 7. The effect of amount of MWCNTs and MWCNTs-DJKA

for aluminum extraction in serum and water samples

Aluminum extraction by MWCNTs-DJKA Farnaz Hosseini et al

increasing sample volume, the extraction

recovery was decreased (Fig. 8).

3.9. The effect of interfernce ions in extraction

The effect of interference of coexisting ions for

aluminum extraction in water and serum samples

was investigated by USA-D-μ-SPE procedure.

So, the different concentrations of the interfering

cations and anions added to 10 mL of aluminum

standard solution based on MWCNTs-DJKA at

in ranges of 0.3-12.8 µg L-1 at pH=5. The results

showed us that the most of the concomitant

ions have no effect on the extraction

recovery of Al (III) ions by USA-D-μ-SPE

procedure (Table 2).

3.10. Validation of methodology

The ultra-trace aluminum in human

serum and water samples were evaluated

by the USA-D-μ-SPE procedure. As

results in Table 3, the Al (III) ions in

human serum and water samples was

efficiently extracted based on MWCNTs-

DJKA with high recovery. The results

showed us that the proposed procedure

was well validated by spiking of standard

solution between 0.3 µg L−1 to 12.8 µg L−1 with

the high accuracy. The obtained recoveries of

spiked samples demonstrated that MWCNTs-

DJKA adsorbent can be used as applied and

simple procedure for aluminum separation in

different samples in short time. Moreover, the

validating of methodology was obtained based

on the standard reference materials (SRM) and

ICP-MS analysis for aluminum determination

in water and serum samples by USA-D-μ-SPE

Fig. 8. The effect of sample volume on aluminum extraction by

USA-D-μ-SPE procedure

Table 3. Method validation for aluminum extraction/

determination in water and serum samples by spiking

samples

Sample Added

(μg L-1)

*Found

(μg L-1)Recovery (%)

Water 1 --- 0.524 ± 0.023 ---

0.5 1.012 ± 0.053 97.6

Water 2

--- 5.536 ± 0.247 ---

5.0 10.602 ± 0.503 101.3

Water 3

--- 6.464 ± 0.288 ---

6.0 12.231 ± 0.573 96.1

Serum 1 --- 0.398 ± 0.021 ---

0.5 0.901 ± 0.043 100.6

Serum 2

--- 3.241 ± 0.152 ---

3.0 6.132 ± 0.332 96.4

Serum 3

--- 7.207 ± 0.346 ---

5.0 12.155 ± 0.574 98.9

*Mean of three determinations of samples ± condence

interval (P = 0.95, n =10)

Interfering Ions (I)

Mean ratio

(CI /C Al(III))Recovery (%)

Pb(II) Pb(II)

Ni2+, Co2+, Cd2+ 600 97.4

Zn2+, Cu2+ 900 98.2

Mo2+, V3+, Cr3+ 700 96.7

Hg2+, Ag+100, 200 98.3

Br-, F-, Cl-, I-900 99.2

Na+, K+1000 99.4

CO3

2-, PO4

3-, NO3

-1100 98.0

Ca2+, Mg2+ 550 97.1

Pb2+, Se2+ 750 96.9

S2-, SO3

2- 850 98.6

Table 2. The effect of interferences ions on extraction

of Al(III) based on MWCNTs-DJKA in water/serum

samples by USA-D-μ-SPE procedure

90 Anal. Method Environ. Chem. J. 3 (2) (2020) 82-91

procedure (Table 4). Analytical results in serum

and water samples were confirmed by SRM and

ICP-MS.

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Table 4. Validation of methodology for aluminum extraction in water and serum samples by the standard

reference materials (SRM) and ICP-MS

Sample Added(μg L-1)*Found(μg L-1) Recovery (%)

SRM 1643 -------- 7.52 ± 0. 34 97.7

5.0 12.36 ± 0. 58 96.8

SRM 1643d -------- 2.61± 0. 12 102.7

2.0 4.54± 0. 19 96.5

a Serum SRM -------- 4.96 ± 0.22 95.4

5.0 9.88 ± 0.48 98.4

*Mean of three determinations of samples ± condence interval (P = 0.95, n =10)

SRM 1643, aluminum in water, 77± 1 μg g-1, 1 g of sample diluted in 100 mL of DW with HNO3 (2%) after dilution

10 mL of stock solution was used as 7.7± 0. 1 μg L-1

SRM 1643d, aluminum in water: 127.6 ± 3.5 μg L-1, after dilution with DW (1:50) was used as 2.54± 0. 08 μg L-1

aICP-MS: Serum aluminum concentration was obtained 5.2 ± 0.11 μg L-1

4. Conclusions

In this study, a novel MWCNTs-DJKA adsorbent

was used for aluminum extraction/separation and

preconcentration from water and human serum

samples in pH=5 by USA-D-μ-SPE procedure.

The ionic liquid of [OMIM][PF6] was dispersed

in samples for separating of MWCNTs-DJKA

from liquid phase. The adsorption capacity of

the MWCNTs-DJKA and MWCNTs sorbent was

achieved 122.6 mg g-1 and 33.7 mg g-1 for 20

min, respectively. The mean aluminum in

drinking water and serum samples was obtained

48.56 ± 2.92 and 11.64 ± 0.73 μg L-1 which was

lower than reference value in drinking water and

human biological samples. The methodology

was validated with SRM and ICP-MS analyzer.

5. Acknowledgment

The authors are thank to the Iranian Petroleum

Industry Health Research Institute and IAUPS

for preparation human serum samples based on

the world medical association declaration of

Helsinki (R.IAU.SN.1396.944000978)

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