1. Introduction

Nickel is the 28th element of Periodic table that

found in abundance the earth’s crust

[1-4]. Pure

nickel is a hard, silvery white, lustrous, malleable,

ductile, shining metal with high electrical and

thermal conductivity

[2,5]. The soluble nickel salts

and metallic nickel, nickel sulphides and nickel

oxides are poorly water soluble

[2]. Nickel as a heavy

metal, nonessential great environmental concern

because widely occurring in the environment from

various natural sources including emissions from

fossil fuel consumption and anthropogenic processes

including modern technologies and production

of products such as coins, jewelry, stainless steel,

batteries, medical devices, plating and welding

[6-

. In 2008, nickel received the shameful name of

the “Allergen of the Year”

[8]. Humans are exposed

to nickel in both occupational and Non-occupational

forms. Occupational exposure to Nickel is primarily

associated with workers in the producing and using of

Nickel in industry sectors. Non-occupational sources

of nickel exposure include is food, air and water.

Human exposure to nickel occurs of inhalation,

dermal contact, and gastrointestinal primary routes.

Some speciﬁc aspects of nickel toxicities include

Genotoxicity, Developmental toxicity, Neurotoxicity,

Haematotoxicity, Immunotoxicity, Neurotoxicity

Facile synthesis of a modiﬁed HF-free MIL-101(Cr)

nanoadsorbent for extraction nickel in water and

wastewater samples

Saeed Fakhraie

a,*

and Ali Ebrahimi

Chemistry Department, Yasouj University, P.O. Box 74831-75918, Yasouj, Iran

Occupational Health Engineering Department, School of Public Health, Qom University of Medical Sciences, Qom, Iran

ABSTRACT

A novel sorbent based on MIL-101(Cr) nanoadsorbent as a MOF

structure was used for nickel extraction from water and wastewater

samples. In this study, 30 mg of MIL-101(Cr) nanoadsorbent

dispersed in 50 mL of water or wastewater samples, after sonication

and adjusting pH =8.5, the nickel ions was extracted by carboxyl

groups of terephthalic acid (MOF(C

(COO)

…. Ni

) by

dispersive suspension-micro solid-phase extraction (DS--SPE).

The MOF was separated from liquid phase with ﬁlter membrane (0.2

m), eluted with 0.5 mL of nitric acid as back-extraction solution and

ﬁnally, the nickel concentration in elution was determined by atom

trap-ﬂame atomic absorption spectrometry (AT-FAAS) after dilution

with DW up to 1 mL. The LOD, the linear range and preconcentration

factor were achieved 1.5 g L

1

, 5-160 g L

1

and 49.7, respectively.

The absorption capacity of MOF for nickel was obtained 136.8 mg

-1

. The results of procedure were validated by spiking of samples and

ET-AAS analyzer.

Keywords:

MIL-101(Cr) nanoadsorbent,

Nickel,

Water and wastewaters,

Dispersive suspension micro solid phase

extraction,

Atom trap-ﬂame atomic absorption

spectrometry

Anal. Method Environ. Chem. J. 3 (2) (2020) 59-73

ARTICLE INFO:

Received 16 Feb 2020

Revised form 12 Apr 2020

Accepted 8 May 2020

Available online 28 Jun 2020

Corresponding Author: Saeed Fakhraie

Email: saeedfakhraie@yahoo.com

https://doi.org/10

Research Article, Issue 2

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

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

Anal. Method Environ. Chem. J. 3 (2) (2020) 59-73

and Carcinogenicity is [2, 4, 5, 8-11]. The adverse

health effects of nickel for humans depend on

the route of exposure, water solubility of nickel

compounds, dose, bodyweight, sensitivity

and exposure periods

[10]. Exposure to nickel

causes irritation of the nose, vertigo, insomnia,

sinuses and loss of sense of smell, headache,

nausea, vomiting, chest pain, nonproductive

cough, dyspnoea, cyanosis, abdominal pain,

diarrhea, tachycardia, palpitations, sweating,

visual disturbances, weakness, lassitude and

shortness of breath, giddiness and it could also

lead to asthma, bronchitis and other respiratory

diseases, eventually causing lung cancer

[4,8,12].

According to the Research on Cancer (IARC)

and the U.S. Department of Health nickel sulfate,

sulﬁdes and oxides combinations of nickel are

be classiﬁed in Group 1, (i.e. cancerogenic to

humans) and metallic nickel in Group 2B, (i.e.

Possibly carcinogenic to humans

[2,5,8,13].

The Permissible Exposure Limit (PEL) by

Occupational Safety and Health Administration

(OSHA) for dust, fume and metal of nickel

and Recommended Exposure Limit (REL) by

National Institute of Occupational Safety and

Health (NIOSH) for metal and soluble of nickel

are 1and 0.015 mg m

respectively. In addition,

World Health Organization (WHO) has proposed

a guideline value of 20 g L

-1

for the maximum

permissible concentration of nickel in drinking

water

[14, 15]. A variety of methods such as

cloud point extraction (CPE)

[16-20], ionic

liquid dispersive liquid-liquid micro extraction

(IL-DLLME)

[18,21], liquid–liquid extraction,

cold induced aggregation microextraction

(CIAME)

[15], Solid phase extraction (SPE)

[22-26], ligandless-ultrasound-assisted

emulsiﬁcation microextraction (USAEME)

[27],

coupled to various instrumental techniques like

ﬂame atomic absorption spectrometry (FAAS)

[16,23,28,29,30-32] graphite furnace atomic

absorption spectrometry (GFAAS)

[33-34],

ultrasonic nebulizer and inductively coupled

plasma optic emission spectrometry (USN-ICP-

OES)

[17], inductively coupled plasma atomic

emission (ICP AES)

[35], UV spectrometry

[36], X-ray ﬂuorescence spectrometry [37],

inductively coupled plasma optic emission

spectrometry (ICP-OES)

[21], high performance

liquid chromatography (HPLC)

[38], inductively

coupled plasma optic emission spectrometry

(ICP-OES), have been developed for the for

preconcentration and determination of nickel at

low concentrations

[39]. During the last decade,

metal-organic frameworks (MOFs) have widely

attracted international attention due to their

high thermal stability, large surface area, and

pore volume. Although a variety of MOFs has

been developed, having their own particular

properties, MIL (standing for materials of institute

Lavoisier) structures have been more intriguing

than other constituents owing to their extra-

large cavities, high moisture stability, and lower

production cost. For the ﬁrst time, Ferey and his

colleagues succeeded to synthesize nanoporous

chromium terephthalate MIL-101(Cr) with a 3D

structure by incorporating ter- ephthalic acid

(benzene-1,4-dicarboxylic acid), chromium salt

(Cr (NO

)

·9H

O) and hydroﬂuoric acid (HF),

as a modulator, in an aqueous medium

[40]. In

addition to the substantially large surface area

and pore volume, they displayed that MIL-

101(Cr) has an exclusive pore size distribution

with two types of inner cages (29 Å and 34 Å)

and windows (12*12 Å and 14.7*16 Å). These

promising features have unprecedentedly

boosted the role of MIL-101(Cr) and its

derivatives in the gas storage (CO

[43–44],

[45–49] and H

[50–53]), gas separation

(CO

/CH

[54–56] and CO

[57–59]) and

catalytic applications

[60–63].

2. Material and Methods

2.1. Instrumental

The nickel concentration was determination by

spectra GBC 906 double beam atom trap ﬂame

atomic absorption spectrophotometer with

deuterium lamp as a background correction (AT-F

AAS, GBC, Aus). The atom trap was installed on

an air-acetylene burner. The operating software of

MIL-101(Cr) nanoadsorbent for extraction nickel in waters Saeed Fakhraie et al

AVANTA was utilized for collecting and storing

data. A HCL of nickel adjusted at a current of 4.0

mA and a wavelength of 232.0 nm with a spectral

bandwidth of 0.2 nm. The working range for

nickel was obtained 0.5 -8 mg L

-1

. The pH-meter

(Metrohm 744 Switzerland), centrifuge (EBA,

Germany) and ultrasonic bath (Kunshan) were

used.

2.2. Reagents and Materials

In the synthesis procedure, chemicals including

Chromium nitrate nonahydrate (Cr(NO

)3.9H

97%), 1, 4-benzene dicarboxylic acid (H

BDC),

Methanol (MeOH, Merck, 99.9%), ethanol (EtOH,

Merck, 99.9%), N, N-dimethylformamide (DMF,

Merck, 99.8%) and Acetone were purchased from

commercial vendors and utilized as received. (DI)

water was employed as solvents. All reagents

with analytical grade purchased from Merck

(Darmstadt, Germany). Stock solutions of Ni(II)

were prepared by dissolving powder amounts of

Ni(NO

)

in deionized water (DW). The standard

solutions were prepared daily by diluting with

deionized water. Deionized water prepared from

Milli-Q plus water from Millipore, USA. The pH

of solutions was adjusted by ammonium chloride

(NH

/NH

Cl) for pH 8–10. All the laboratory

glasses were cleaned by 10% (v/v) nitric acid for

24 h and washed with DW 10 times.

2.3. Preparation of MIL-101(Cr) nanoparticles

In a typical procedure, 16 g of Cr(NO

)

.9H

and 6.56 g of terephthalic acid were separately

added to deionized water (200 mL) and mixture

was intensively stirred for 30 min with a magnetic

stirrer. The resulting mixture was transferred to a

stainless steel autoclave and heated at 220 °C for 18

h. Upon heating, the mixture became as a soft green

powder which was washed ﬁve times with boiling

deionized water, three times with MeOH and three

times with acetone in order to remove impurities

and unreacted materials. In addition, to separate

the remained terephthalic acid, the resulting solid

was suspended in 50 mL of dimethylformamide

and kept at 70°C overnight. After cooling, the

sample was washed by pure ethanol for three times

and the resulting powder was dried at 100 °C for

24 h to obtain the ﬁnal product.

2.4. Characterization

To investigate the crystallinity and phase structure

of the samples, powder X-ray diraction (PXRD)

method was considered by using Philips PW-1730

instrument with Cu-K radiation ( = 1.5406 Å).

The scanning rate was 1 deg/min and operating

power was 40 kV and 40 mA. To determine the

functional groups, Fourier transform infrared

spectroscopy (FT-IR) was performed using Bruker

(VERTEX 70) spectrum from 400 to 4000 cm

-1

Field Emission Scanning Electron Microscopy (FE-

SEM) studies were carried out with a JEOL JEM

3010 instrument under 15 kV voltage and 50

kx and 100 kx magniﬁcations. The speciﬁc surface

area, total pore volume, average pore width and

pore size distribution measurements was performed

with a Micrometrics ASAP-2010 instrument by

adsorption of nitrogen at 77 K. Before analysis,

the sample was degassed at 175°C and vacuum

pressure for 2 h to remove moisture, solvents and

other unwelcome molecules from pores.

2.5. Analytical Procedure

By DS--SPE procedure, the nickel ions were

separated/preconcentrated from 50 mL of

wastewater based on MIL-101(Cr) as MOF

nanoadsorbent. First, the pH of wastewater

samples and standard nickel solution containing 1-

400 g L

1

was adjusted up to 8.5 with phosphate

or ammonium chloride buffer before adding 30 mg

of MIL-101(Cr). After shaking in ultrasonic bath

for 5 min at room temperature (50 kHz, 100 W),

the nickel ions was extracted by carboxyl groups

of MIL-101(Cr). Then the MIL-101 sorbent was

separated from liquid phase with ﬁlter membrane

(0.2 m) based on vacuum accessory and eluted

with 0.5 mL of nitric acid as back-extraction

solution. Finally, the nickel concentration in

eluent was determined by atom trap-ﬂame atomic

absorption spectrometry (AT-FAAS) after dilution

with DW up to 1 mL

(Fig. 1).

Anal. Method Environ. Chem. J. 3 (2) (2020) 59-73

Fig.1.

Nickel extraction based on MIL-101(Cr) from wastewater samples by DS--

SPE procedure

Fig.2. The robust framework of MIL-101 based on chromium (III) octahedral clusters

Fig.3. The structure of two types of mesoporous cages in MIL-101 with pentagonal

forms

3. Results and discussion

F´erey et al. prepared MIL-101 (MIL, Mat´erial

Institut Lavoisier) with a chemical composition

of {Cr

F (H

O) 2O (BDC) 3. nH

O} (n 25; 1,

4-benzenedicarboxylate (BDC) and superior

physicochemical properties. The robust framework

of MIL-101 was comprised of trimeric chromium

(III) octahedral clusters interconnected by BDC

molecules resulting in an augmented MTN zeotype

structure

(Fig. 2).

This structure was comprised of two types of

mesoporous cages with diameters of ~29 and 34 Å

accessible through two types of microporous windows

(the smaller cages have pentagonal windows with a

free opening of ~12 Å, while the larger cages possess

both pentagonal and hexagonal windows with a

~14.7 Å by 16 Å free aperture)

(Fig. 3).

3.1. Extraction Mechanism

The material exhibits excellent stability against

moisture and other chemicals, and the terminal

water molecules in MIL-101 can be removed by

heating in air or under vacuum at 423 K, which

generates two coordinatively unsaturated open

metal sites (CUS) per trimeric Cr(III) octahedral

cluster. In addition to its highly porous nature,

MIL-101 has attracted considerable attention

because functional modiﬁcations on MIL-101

can be achieved easily either directly using

a functionalized ligand during the synthesis

or indirectly via the diverse post-synthesis

chemical treatment on the CUS or on the organic

linkers. Among the MOFs known, MIL-101 is

one of the most promising porous materials for

future energy and environmental applications,

surpassing MOF-5 or HKUST-1, owing to its

superior physicochemical properties including

high hydrothermal/chemical stability and

desirable textural properties. Due to MIL-101

Structure nickel was physically and chemically

extracted based on porous materials in MIL-101

nanostructure and covalence bonding by carboxyl

groups of terephthalic acid (MOF-(C

(COO)

….Ni

) , respectively (Fig. 4).

MIL-101(Cr) nanoadsorbent for extraction nickel in waters Saeed Fakhraie et al

Fig. 4. The extraction mechanism of nickel by MIL-101 nanostructure

3.2. PXRD patterns

PXRD pattern of the MIL-101(Cr) sample, prepared

without modulators, is depicted in

Figure 5. As it

stated, MIL-101(Cr) possessed the most intensive

peaks, as an indicator of the most crystallinity.

The negligible peaks at around 2 = 17.4°, 25.2°

or 27.9° afﬁrmed successful removal of unreacted

BDC crystals from the sample framework

[36]. Moreover, the main diraction peaks of MIL-

101(Cr) (2  5.25°, 8.55°, 9.15°, and 16.58°) was

thoroughly compatible with the MIL-101-HF-1, as

a general reference for MIL-101(Cr).

3.3. FE-SEM

The morphology of the prepared MIL-101(Cr)

sample was characterized by ﬁeld emission

scanning electron microscope (FE-SEM)

analysis. As it is seen in

Figure 6, the image

of MIL-101(Cr) shows highly crystalline

octahedral morphology for this material which

was compatible with the reported MIL-101(Cr)

structures. In addition, there were no needle-

shaped crystals in the images representing the

complete removal of H

BDC crystals by the post-

puriﬁcation process.

Anal. Method Environ. Chem. J. 3 (2) (2020) 59-73

Fig. 5. The PXRD pattern of the MIL-101(Cr) sample Fig. 6. The morphology of MIL-101(Cr) by ﬁeld

emission scanning electron microscope (FE-SEM)

3.4. FT-IR

FT-IR spectra of the synthesized MIL-101(Cr)

illustrated in

Figure 7. In this spectrum the peak

around of 570 cm

-1

was assigned to the Cr–O

stretching vibration, reﬂecting the formation of

MIL-101(Cr) structure. The peaks of between 600

and 1600 cm

-1

were indicated to H

BDC and its

aromatic rings. The bands at 750, 884, 1160 cm

-1

were

attributed to the C–H bond in CH

group and the peak

observed at 1508 cm

-1

indicates the C=C stretching.

A strong band at 1404 cm

-1

is related to O–C–O

symmetric vibrations and showing the dicarboxylate

moiety in the sample. The typical bands located

at 1625 and 3400 cm

-1

conﬁrmed the presence of

hydroxyl groups or moisture in the sample. The FT-

IR results were in accordance to the previous reports

FT-IR patterns which could be an evidence for the

formation of MIL-101(Cr) structures

(Fig. 7).

3.5. Physical properties

To determine physical properties of synthesized

MIL-101(Cr) sample, the N

sorption test at 77 K was

carried out. The related N

sorption isotherms along

with the pore size distribution graphs are depicted in

Figure 8. According to Figure 9-11, the N

sorption

isotherms exhibit the typical type I curve with sharp

adsorption at low partial pressures (P/P0 < 0.01)

and a H

hysteresis loop. In addition, the adsorbents

have conical pores and crystals were composed of

the microporous structure. The speciﬁc surface area

and pore volume of MIL-101(Cr) were calculated

and summarized in

Table 1. The results indicated that

MIL-101(Cr) possessed the BET surface area (2155

-1

) and the BarrettJoynerHalenda (BJH) pore

size distribution curve (b) derived from adsorption

data of the isotherms indicates a main peak with

average pore width of 2.1 for MIL-101(Cr). The

result implies the microporous nature of samples

and is in agreement with the results deduced from

nitrogen adsorption-desorption isotherms and pore

size distribution.

MIL-101(Cr) nanoadsorbent for extraction nickel in waters Saeed Fakhraie et al

Fig. 7. FT-IR spectra of the synthesized MIL-101(Cr)

Fig. 8. Adsorption/desorption isotherm of Cr-MOF

adsorbent with adsorptive of N

at 77oK

3.6. Optimization

The DS--SPE procedure based on Cr-MOF

adsorbent was applied for speciation and

preconcentration of nickel in water samples. For

optimization many parameters such as amount

of sorbent, volume of samples, shaking time,

interference Ions and pH were optimized.

3.6.1.Amount of sorbent

For efﬁcient extraction of nickel, the amount of

MIL-101(Cr) nanoadsorbent was studied. For

this purpose, the amounts of 5 - 50 mg of MIL-

101(Cr) were used for nickel extraction by the

DS--SPE method. The results showed, the high

recoveries between 95-105% were obtained in

wastewater samples with 28 mg of MIL-101(Cr)

for Ni extraction. Therefore, 30 mg of MOF

was used as optimum mass for Ni extraction at

pH=8.5

(Fig. 12).

3.6.2.Volume of samples

The sample volume for nickel extraction

based on MOF was evaluated by DS--SPE

method. In this study the vary volume of

wastewater samples between 5-100 mL was

studied and optimized for 5-160 g L

1

nickel concentration. Based on results, the

efficient extractions were achieved for 55 mL

of wastewater samples. Therefore, 50 mL blood

sample was selected as the optimal sample

volume for further study

(Fig. 13).

3.6.3.The Shaking time

The time of extraction depended on the sonication

of MIL-101(Cr) nanoadsorbent in the wastewater

samples, which was increased interaction between

carboxyl group of MIL-101(Cr) with Ni(II) at

Anal. Method Environ. Chem. J. 3 (2) (2020) 59-73

Fig. 9. BET plot of Cr-MOF adsorbent with adsorptive

of N

at 77

Fig. 10. BJH plot of Cr-MOF adsorbent for absorption

branch at 77

Fig. 11. BJH-plot of Cr-MOF adsorbent for desorption

branch at 77

Table 1. Physical properties of Cr-MOF (MIL-101(Cr))

adsorbent

Product

BET

Surface

area

-1

)

Average

pore

width

(nm)

(cm³ g

-1

)

Total pore

volume

(cm³ g

-1

)

MOF 2155 2.1 495 1.13

pH=8.5. By dispersion of the MIL-101(Cr), the

mass-transference and extraction was performed.

So, the effect of shaking time was studied for

1-20 min. By results, the sonication of 5.0 min

had efﬁcient extraction for Ni ions in wastewater

samples for 30 mg of sorbent. Therefore, 5.0

minute was used as the optimum shaking time by

DS--SPE procedure.

3.6.4.The pH effect

The pH has main role for nickel extraction by

MIL-101(Cr) nanoadsorbent. So, the effect of

different pH (2-11) for extraction of Ni (II) in

wastewater samples were investigated by DS--

SPE procedure. The results demonstrated that the

MIL-101(Cr) as MOF sorbent could be efﬁciently

captured Ni (II) in pH of 8-8.5. Also, the recoveries

MIL-101(Cr) nanoadsorbent for extraction nickel in waters Saeed Fakhraie et al

Fig. 12. The effect of MOF amount for Ni(II) extraction from water samples

Fig.13. The effect of sample volume for Ni(II) extraction from water samples

for Ni (II) based on Cr-MOF were obtained more

than 95% in pH 8.5 and the decreased at lower and

higher pH (7.5>pH>9). So, pH=8.5 was selected

for further experiments

(Fig. 14). The mechanism

of nickel extraction depend on the coordination of

covalent bond of sorbent [Ni

 (COO)

] with the

positively charged of nickel.

3.6.5.Validation

The validation of DS--SPE procedure based

on MOF was obtained by spiking samples. The

different concentration of nickel added to real

samples as lower and upper ranges in wastewater

and water samples. The results showed a good

recovery between 95%-106% which was shown in

Table 2. Also, the validation was conﬁrmed with

electrothermal atomic absorption spectrometry

(ET-AAS) coupled with microwave digestion

process

(Table 3). Based on results in Tables 2 and

3, the nickel ions were efﬁciently extracted by Cr-

MOF adsorbent in optimized conditions.

Anal. Method Environ. Chem. J. 3 (2) (2020) 59-73

Fig. 14. The effect of pH for Ni(II) extraction based on MOF from water samples

Table 2. The validation of DS--SPE procedure based on MOF for nickel(II) extraction from water samples

Samples Added (g L

1

) *Found (g L

1

) Recovery (%)

Water ------ 86.75 ± 3.55 ------

100 185.63 ± 8.73 98.8

Tab water ------ 6.22 ± 0.34 ------

5 11.53 ± 0.48 106.2

Wastewater ------ 144.62 ± 6.13 ------

150 288.49 ± 13.26 95.9

Well water ------ 38.54 ± 2.05 ------

40 77.68 ± 3.06 97.8

Mean of three determinations ± cconﬁdence interval (P= 0.95, n=8)

Wastewater samples diluted with DW (1:1)

3.6.6. Discussions

For metal determination with the DS--SPE

procedure based on Cr-MOF adsorbent, the effect

of the main parameters, such as amount of sorbent,

volume of samples, shaking time, interference Ions

and pH were optimized thoroughly. Results this

study revealed that MIL-101(Cr) nanoadsorbent

was used as a novel sorbent for dispersive

suspension micro solid phase extraction (DS--

SPE) nickel from environmental waters. In in study

highly crystalline octahedral morphology of MIL-

101(Cr) sample as reported MIL-101(Cr) structures

in other studies was characterized by ﬁeld emission

scanning electron microscope (FE-SEM) analysis

[64,65]. FT-IR characterization was conducted to

detect the identity of the MIL-101(Cr) functional

groups that the FT-IR results were in accordance

to the previous reports

[59, 64-66]. In this study,

optimum mass of MOF, pH and time for Ni

extraction 30 mg, 7.5 and 5 minute at pH: 7.5, 30

respectively were obtained in wastewater samples

so that Behbahani, M., et al. this parameters for

Modiﬁcation of magnetized MCM-41 by pyridine

groups for ultrasonic-assisted dispersive micro-

solid-phase extraction of nickel ions 24 mg, 7.5 and

8 minute has been reported

[67]. Based on results,

under optimized conditions detection limit, the

linear range were achieved of 1.5 g L

1

, 5-160 g

1

. In study safavi et al. linear range for 2-amino-

cyclopentene-1-dithiocarboxylicacid absorbent

and Cloud point extraction method linear in the

range of 20–500 g L

1

Obtained [22]. The ﬁndings

of this study showed that MIL-101(Cr) as a valid

procedure for extraction nickel in water samples

can be used.

4. Conclusions

The MIL-101(Cr) as a MOF nanoadsorbent was

synthesized and used for nickel extraction from

water samples by DS--SPE procedure. After

extraction nickel ions with MOF adsorbent at

pH=8.5, it was back-extracted from adsorbent

and ﬁnally, the concentration was determined by

AT-FAAS. The low LOD of 1.5 g L

1

and the

favorite linear range 5-160 g L

1

was achieved.

The high absorption capacity of 136.8 mg g

-1

was

obtained by MIL-101(Cr). The efﬁcient, simple

and fast extraction was achieved in low time by

DS--SPE procedure. The MIL-101(Cr) as solid-

phase had high recovery more than 97% for Ni(II)

extraction from waters without any chelating

agents. Therefore, extraction of nickel based on

MIL-101(Cr) nanoadsorbent for extraction nickel in waters Saeed Fakhraie et al

Table 3. Validation of methodology for nickel extraction from water samples by comparing to ET-AAS coupled

with microwave digestion process

Samples Added (g L

1

)

Found ETAAS

(g L

1

)

Found AT-FAAS

(g L

1

)

Recovery

ETAAS (%)

Recovery AT-

FAAS (%)

Water 1 ------ 10.56± 0.43 10.18± 0.52 ------ ------

10 20.31 ± 0.86 19.87 ± 0.93 97.5 96.9

Water 2 ------ 33.82 ± 1.57 31.95 ± 1.63 ------ ------

30 62.98 ± 2.78 60.88 ± 3.02 97.2 96.4

Water 3 ------ 75.21 ± 3.26 73.93 ± 3.39 ------ ------

50 125.73 ± 6.03 122.86 ± 6.24 101.1 97.8

Water 4 ------ 93.12 ± 4.16 94.27 ± 4.43 ------ ------

100 191.62 ± 8.94 194.77 ± 9.24 98.5 100.5

Mean of three determinations ± cconﬁdence interval (P= 0.95, n=8)

Water1: Darband River,

Water 2: Hesarak River

Water 3: DarAbad River

Water 4: Zaferaniyeh and Velenjak River

MIL-101(Cr) can be used as efﬁcient procedure

for determination and separation of Ni(II) in water

samples by AT-FAAS

5. Acknowledgements

The authors wish to thank Qom University of

Medical Sciences, Qom, Iran, Iranian Petroleum

Industry Health Research Institute (IPIHRI), and

the Iranian Research Institute of Petroleum Industry

(RIPI) for supporting of this work.

6. References

[1] E. Nieboer, J.O. Nriagu, Nickel and human

health, International Conference on nickel

metabolism and toxicology, Espoo, Finland.

Wiley, 1992.

[2] K.K. Das, S.N. Das, S. A. Dhundasi, Nickel:

molecular diversity, application, essentiality

and toxicity in human health, Biometals:

molecular structures, binding properties and

applications, Nova Sci. Publishers, (2010) 33-

58.

[3] A. Arita, M. Costa, Epigenetics in metal

carcinogenesis: nickel, arsenic, chromium and

cadmium, Metallomics, 3 (2009) 222-228.

[4] K.S. Cameron, B. Virginia, B.T. Paul, Exploring

the molecular mechanisms of nickel-induced

genotoxicity and carcinogenicity: a literature

review, Rev. Environ. Health, 2 (2011) 81-92.

[5] K.K. Das, S.N. Das, S. A. Dhundasi, Nickel,

its adverse health effects & oxidative stress,

Indian J. Med. Res., 4 (2008) 412.

[6] A. Arita, M. Costa, Epigenetics in metal

carcinogenesis: nickel, arsenic, chromium and

cadmium, Metallomics, 3 (2009) 222-228.

[7] P.C. Nagajyoti, K.D. Lee, T.V.M. Sreekanth.

Heavy metals, occurrence and toxicity for

plants: a review, Environ. Chem. lett., 3 (2010)

199-216.

[8] A. Duda-Chodak, U. Blaszczyk, The impact of

nickel on human health, J. Elem., 4 (2008) 685-

693.

[9] S. Buxton, E. Garman, K.E. Heim, T. Lyons-

Darden, C. E. Schlekat, M. D. Taylor, A.R.

Oller, Concise review of nickel human health

toxicology and ecotoxicology, Inorganics, 7

(2019) 89.

[10] N. Alam, S.J. Corbett, H.C. Ptolemy,

Environmental health risk assessment of nickel

contamination of drinking water in a country

town in NSW, New South Wales Public Health

bull., 10 (2008) 170-173.

[11] M.G. Permenter, J.A. Lewis, D.A. Jackson,

Exposure to nickel, chromium, or cadmium

causes distinct changes in the gene expression

patterns of a rat liver derived cell line, PLOS

one, 11 (2011) e27730.

[12] F. Akbal, S. Camcı, Copper, chromium and

nickel removal from metal plating wastewater

by electrocoagulation, Desalination, 3 (2011)

214-222.

[13] K. Bhupander, D.P. Mukherjee, Assessment of

human health risk for arsenic, copper, nickel,

mercury and zinc in ﬁsh collected from tropical

wetlands in India, Adv. Life Sci. Technol., 2

(2011) 13-24.

[14] NIOSH Manual of analytical methods (NMAM,

5 Edition), U.S. department of health and

human services, 2015.

[15] H. Abdolmohammad-Zadeh, E. Ebrahimzadeh.

Ligandless cloud point extraction for trace

nickel determination in water samples by ﬂame

atomic absorption spectrometry, J. Brazilian

Chem. Soc., 3 (2011) 517-524.

[16] C.A. ahin, M. Efeçınar, N. atırolu.

Combination of cloud point extraction and

ﬂame atomic absorption spectrometry for

preconcentration and determination of nickel

and manganese ions in water and food samples,

J. Hazard. Mater., 3 (2010) 672-677.

[17] A. Safavi, H. Abdollahi, M.R. Hormozi

Nezhad, R. Kamali, Cloud point extraction,

preconcentration and simultaneous

spectrophotometric determination of nickel

and cobalt in water samples, Spectrochim.

Acta Part A: Mol. Biomol. Spec., 12 (2004)

2897-2901.

[18] J. Chen, K.C. Teo, Determination of cobalt

and nickel in water samples by ﬂame atomic

absorption spectrometry after cloud point

Anal. Method Environ. Chem. J. 3 (2) (2020) 59-73

extraction, Anal. Chim. Acta, 2 (2001) 325-330.

[19] J.L. Manzoori, G. Karim-Nezhad, Development

of a cloud point extraction and preconcentration

method for Cd and Ni prior to ﬂame atomic

absorption spectrometric determination, Anal.

Chim. Acta, 2 (2004) 173-177.

[20] C. Fan, Q. Pan, Q. Li, L. Wang, Cloud point-

TiO 2/sepiolite composites extraction

for simultaneous preconcentration and

determination of nickel in green tea and

coconut water, J. Iran. Chem. Soc., 2 (2016)

331-337.

[21] S.M.N. Moalla, A.S. Amin. An ionic liquid-based

microextraction method for highly selective

and sensitive trace determination of nickel in

environmental and biological samples, Anal.

Method., 24 (2015) 10229-10237.

[22] A. Moghimi, M.J. Pourshariﬁ, Perconcentration

of Ni (II) from sample water by modiﬁed nano

ﬁber, Oriental J. Chem., 1 (2012) 353.

[23] S.Z. Mohammadi, D. Afzali, Y.M. Baghelani.

Flame atomic absorption spectrometry

determination of trace amounts of nickel ions

in water samples after ligandless ultrasound-

assisted emulsiﬁcation microextraction, Anal.

Sci., 9 (2010) 973-977.

[24] V.A. Lemos, G.S. Do Nascimento, L.S. Nunes, A

new functionalized resin for preconcentration

and determination of cadmium, cobalt, and

nickel in sediment samples, Water, Air, Soil

Pollut., 2 (2015) 2.

[25] H. Shirkhanloo, M. Falahnejad, H. Zavvar

Mousavi, Mesoporous silica nanoparticles

as an adsorbent for preconcentration and

determination of trace amount of nickel in

environmental samples by atom trap ﬂame

atomic absorption spectrometry, J. Appl. Spec.,

6 (2016) 1072-1077.

[26] H. Sereshti, V. Khojeh, M. Karimi, S. Samadi,

Ligandless-ultrasound-assisted emulsiﬁcation-

microextraction combined with inductively

coupled plasma-optical emission spectrometry for

simultaneous determination of heavy metals in

water samples, Anal. Method., 1 (2012) 236-241.

[27] V.A. Lemos, V.J. Ferreira, J.A. Barreto,

L.A. Meira, Development of a method

using ultrasound-assisted emulsiﬁcation

microextraction for the determination of nickel

in water samples, Water, Air, Soil Pollut., 5

(2015) 141.

[28] M. Karimi, S. Dadfarnia, A.M.H. Shabani,

Application of deep eutectic solvent modiﬁed

cotton as a sorbent for online solid-phase

extraction and determination of trace amounts

of copper and nickel in water and biological

samples, Biol. Trace Elem. Res., 1 (2017) 207-

215.

[29] M.R. Jamali, A. Madadjo, R. Rahnama.

Determination of nickel using cold-induced

aggregation microextraction based on ionic

liquid followed by ﬂame atomic absorption

spectrometry, J. Anal. Chem., 5 (2014) 426-

431.

[30] J.L. Manzoori, G. Karim-Nezhad, Development

of a cloud point extraction and preconcentration

method for Cd and Ni prior to ﬂame atomic

absorption spectrometric determination, Anal.

Chim. Acta, 2 (2004) 173-177.

[31] A.A. Gouda, A.M. Summan, A.H. Amin,

Development of cloud-point extraction method

for preconcentration of trace quantities of

cobalt and nickel in water and food samples,

RSC Adv., 96 (2016) 94048-94057.

[32] T.G. Kazi, H.I. Afridi, N. Kazi, M.K. Jamali,

M.B. Arain. Copper, chromium, manganese,

iron, nickel, and zinc levels in biological

samples of diabetes mellitus patients, Biol.

Trace Elem. Res., 1 (2008) 1-18.

[33] F.A. Lobo, D. Goveia, A.P. Oliveira, L.P.C.

Romão, Development of a method to

determine Ni and Cd in biodiesel by graphite

furnace atomic absorption spectrometry, Fuels,

1 (2011) 142-146.

[34] P. Liang, L. Peng, “Determination of nickel

in water samples by graphite furnace atomic

absorption spectrometry after ionic liquid-

based dispersive liquid-liquid microextraction

preconcentration, Atom. Spec., 2 (2012) 53-58.

[35] Y Xu, J Zhou, G Wang, J Zhou, G Tao,

Determination of trace amounts of lead,

MIL-101(Cr) nanoadsorbent for extraction nickel in waters Saeed Fakhraie et al

arsenic, nickel and cobalt in high-purity iron

oxide pigment by inductively coupled plasma

atomic emission spectrometry after iron matrix

removal with extractant-contained resin, Anal.

Chim. Acta, 1 (2007) 204-209.

[36] F. Zhou, C. Li, H. Zhu, Y. Li, A novel method

for simultaneous determination of zinc,

nickel, cobalt and copper based on UV–VIS

spectrometry, Optik, 182 (2019) 58-64.

[37] X. Lu, L. Wang, K. Lei, J. Huang, Y. Zhai,

Contamination assessment of copper, lead, inc,

manganese and nickel in street dust of Baoji,

NW China, J. Hazard. Mater., 3 (2009) 1058-

1062.

[38] Q. Zhou, A. Xing, K. Zhao, Simultaneous

determination of nickel, cobalt and

mercury ions in water samples by solid

phase extraction using multiwalled carbon

nanotubes as adsorbent after chelating with

sodium diethyldithiocarbamate prior to

high performance liquid chromatography, J.

Chromatogr. A, 1360 (2014) 76-81.

[39] Q. Han, Y. Huo, L. Yang, X. Yang, Y. He, J.

Wu, Determination of trace nickel in water

samples by graphite furnace atomic absorption

spectrometry after mixed micelle-mediated

cloud point extraction, Molecules, 10 (2018)

2597.

[40] G. Férey, C. Mellot-Draznieks, C. Serre, F.

Millange, J. Dutour, S. Surble, I. Margiolaki,

A chromium terephthalate-based solid with

unusually large pore volumes and surface area,

Sci., 309 (2005) 2040–2042.

[41] M.S. Alivand, M. Shaﬁei-Alavijeh, Tehrani

NHMH, E. Ghasemy, A. Rashidi, S. Fakhraie,

Facile and high-yield synthesis of improved

MIL-101(Cr) metal-organic framework with

exceptional CO2 and H

S uptake; the impact

of excess ligand- cluster, Micropor. Mesopor.

Mater., 279 (2019) 153–164.

[42] M. Montazerolghaema, S.F. Aghamiri, S.

Tangestaninejad, M.R. Talaie, Metal-or-

ganic framework MIL-101 doped with metal

nanoparticles (Ni & Cu) and its eect on CO2

adsorption properties, RSC Adv., 6 (2016)

632–640.

[43] S. Pourebrahimi, M. Kazemeini, L. Vafajoo,

Embedding graphene nanoplates into MIL-

101(Cr) pores: synthesis, characterization, and

CO2 adsorption studies, Ind. Eng. Chem. Res.,

56 (2017) 3895–3904.

[44] N.A.A. Qasem, N.U. Qadir, R. Ben-Mansour,

S.A.M. Said, Synthesis, characteriza- tion,

and CO2 breakthrough adsorption of a novel

MWCNT/MIL-101(Cr) composite, J. CO2

Util. 22 (2017) 238–249.

[45] P.L. Llewellyn, S. Bourrelly, C. Serre, A.

Vimont, M. Daturi, L. Hamon, G.D. Weireld,

J.S. Chang, D.Y. Hong, Y.K. Hwang, S.H. Jhung,

G. Fe´rey, High uptakes of CO2 and CH4 in

mesoporous metals organic frameworks MIL-

100 and MIL-101, Langmuir J., 24 (2008)

7245–7250.

[46] S. Kayal, B. Sun, A. Chakraborty, Study of

metal-organic framework MIL-101(Cr) for

natural gas (methane) storage and compare

with other MOFs (metal-organic frameworks),

Energ., 91 (2015) 772–781.

[47] K. Munusamy, G. Sethia, D.V. Patil, P.B.S.

Rallapalli, R.S. Somani, H.C. Bajaj, Sorption

of carbon dioxide, methane, nitrogen and

carbon monoxide on MIL- 101(Cr): volumetric

measurements and dynamic adsorption studies,

Chem. Eng. J., 195 (2012) 359-68.

[48] P. Chowdhury, S. Mekala, F. Dreisbach, S.

Gumma, Adsorption of CO, CO2 and CH4

on Cu-BTC and MIL-101 metal organic

frameworks: effect of open metal sites and

adsorbate polarity, Mesopor. Mater., 152

(2012) 246–252.

[49] P.Á Szilágyi, P. Serra-Crespo, J. Gascon, H.

Geerlings, B. Dam, The impact of post-

synthetic linker functionalization of MOFs

on methane storage: the role of defects, Front.

Energ. Res., 4 (2016) 9.

[50] Z. Yu, J. Deschamps, L. Hamon, P.K.

Prabhakaran, P. Pre, Hydrogen adsorption

and kinetics in MIL-101(Cr) and hybrid

activated carbon-MIL-101(Cr) materials, Int.

J. Hydrogen Energ., 45 (2017) 8021–8031.

Anal. Method Environ. Chem. J. 3 (2) (2020) 59-73

[51] A. Malouche, G. Blanita, D. Lupu, J. Bourgon,

J. Nelayah, C. Zlotea, Hydrogen absorption in

1 nm Pd clusters conﬁned in MIL-101(Cr), J.

Mater. Chem., 44 (2017) 23043–23052.

[52] N. Bimbo, W. Xu, J.E. Sharpe, V.P. Ting, T.J.

Mays, High-pressure adsorptive sto- rage

of hydrogen in MIL-101 (Cr) and AX-21

for mobile applications: Cryocharging and

cryokinetics, Mater. Design., 89 (2016) 1086–

1094.

[53] G. Blni, M. Streza, M.D. Lazr, D. Lupu,

Kinetics of hydrogen adsorption in MIL- 101

single pellets, Int. J. Hydrogen Energ., 42

(2017) 3064–3077.

[54] X. Zhou, W. Huang, J. Miao, Q. Xia, Z. Zhang, H.

Wang, Z. Li, Enhanced separation performance

of a novel composite material GrO@MIL-101

for CO2/CH4 binary mixture, Chem. Eng. J.,

266 (2015) 339–344.

[55] M.S. Alivand, F. Farhadi, Multi-objective

optimization of a multi-layer PTSA for LNG

production, J. Nat. Gas Sci. Eng., 49 (2018)

435–446.

[56] Q. Yan, Y. Lin, C. Kong, L. Chen, Remarkable

CO2/CH4 selectivity and CO2 ad- sorption

capacity exhibited by polyamine-decorated

metal-organic framework ad- sorbents, Chem.

Commun., 49 (2013) 6873–6875.

[57] Y. Lin, H. Lin, H. Wang, Y. Suo, B. Li, C. Kong,

L. Chen, Enhanced selective CO2 adsorption

on polyamine/MIL-101(Cr) composites, J.

Mater. Chem. A., 2 (2014) 14658–14665.

[58] Z. Zhou, L. Mei, C. Ma, F. Xu, J. Xiao, Q. Xia,

Z. Li, A novel bimetallic MIL-101(Cr, Mg)

with high CO2 adsorption capacity and CO2/

N2 selectivity, Chem. Eng. Sci., 147 (2016)

109–117.

[59] Q. Liu, L. Ning, S. Zheng, M. Tao, Y. Shi, Y. He,

Adsorption of carbon dioxide by MIL-101(Cr):

regeneration conditions and inﬂuence of ﬂue

gas contaminants, Sci. Rep., 3 (2013) 2916.

[60] Y. Wang, Y. Zhang, Z. Jiang, G. Jiang, Z.

Zhao, Q. Wu, Y. Liu, Q. Xu, A. Duan, C. Xu,

Controlled fabrication and enhanced visible-

light photocatalytic hydrogen pro- duction

of Au@CdS/MIL-101 heterostructure, Appl.

Catal. B: Environ., 185 (2016) 307–314.

[61] X. Li, Y. Pi, Q. Xia, Z. Li, J. Xiao, TiO2

encapsulated in Salicylaldehyde-NH2-MIL-

101(Cr) for enhanced visible light-driven

photodegradation of MB, Appl. Catal. B:

Environ., 191 (2016) 192–201.

[62] M.L. Hu, V. Safarifard, E. Doustkhah, S.

Rostamnia, A. Morsali, N. Nouruzi, S. Beheshti,

K. Akhbari, Taking organic reactions over

metal-organic frameworks as heterogeneous

catalysis, Micropor. Mesopor. Mater., 256

(2018) 111–127.

[63] L. Qin, Z. Li, Z. Xu, X. Guo, G. Zhang, Organic-

acid-directed assembly of iron-carbon oxides

nanoparticles on coordinatively unsaturated

metal sites of MIL-101 for green photochemical

oxidation, Appl. Catal. B: Environ., 179

(2015) 500–508.

[64] M. Shaﬁei, M.S. Alivand, A. Rashidi, A.

Samimi, D. Mohebbi-Kalhori, Synthesis and

adsorption performance of a modiﬁed micro-

mesoporous MIL-101 (Cr) for VOCs removal

at ambient conditions, Chem. Eng. J., 341

(2018) 164-174.

[65] P.B. Rallapalli, M.C. Raj, S. Senthilkumar,

R.S. Somani, H.C. Bajaj, HFfree synthesis

of MIL101 (Cr) and its hydrogen adsorption

studies, Environ. Prog. Sustain. Energ., 2

(2016) 461-468.

[66] N. Tian, The synthesis of mesostructured NH

2-MIL-101 (Cr) and kinetic and thermodynamic

study in tetracycline aqueous solutions, J.

Porous Mater., 5 (2016) 1269-1278.

[67] M. Behbahani, V. Zarezade, A. Veisi, F. Omidi,

S. Bagheri, Modiﬁcation of magnetized MCM-

41 by pyridine groups for ultrasonic-assisted

dispersive micro-solid-phase extraction of

nickel ions, Int. J. Environ. Sci. Technol., 10

(2019) 6431-6440.

MIL-101(Cr) nanoadsorbent for extraction nickel in waters Saeed Fakhraie et al