Anal. Method Environ. Chem. J. 3 (4) (2020) 72-84

Research Article, Issue 4

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

Separation of aniline from water and wastewater samples

based on

activated carbon nanoparticles

and dispersive

solid phase extraction procedure

Saeed Fakhraie

a,*

, Morteza Mehdipour Rabouri

and Ahmad Salarifar

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

Occupational Health Engineering Department, , Kerman University of Medical Sciences, Kerman, Iran

Environmental Engineering, Faculty of Natural Resources, Islamic Azad University, Bandar Abbas Branch, Iran

ABSTRACT

The water, wastewater and air are the main sources of aniline

in environment. Aniline has a toxic effect in the human body and

environment and so, must be determined by novel techniques. In this

study, the

activated carbon with microwave heating methods

(MHM-ACNPs) were used for extraction aniline from waters by

dispersive ionic liquid solid phase extraction procedure (D-IL-SPE)

and compared to the

activated carbon

(AC). For this purpose,

the mixture of acetone, ionic liquid and 30 mg of MHM-ACNPs/

AC added to 100 mL of water samples at pH=8. After sonication

for 10 min, the benzene ring in aniline as

electron acceptor

was

chemically adsorbed on

carboxylic groups of MHM-ACNPs

electron donors

(MHM-ACNPs-COO

─

……C

-NH

) and then,

the adsorbent was collected by hydrophobic ionic liquid phase in

bottom of conical centrifuging tube. Finally, the aniline was released

from MHM-ACNPs in remained solution by changing pH and the

concentration of aniline determined by gas chromatography–ﬂame

ionization detector (GC-FID). The working range (WR) was obtained

from 2.0 to 4000 µg L

-1

(RSD % < 1.8). The detection limit (LOD)

and preconcentration factor (PF) and linear range (LR) were achieve

0.6 µg L

-1

, 196.4 and 2.0─950 µg L

-1

, respectively. The proposed

method was validated by spiking of real samples and analysis with

gas chromatography mass detector (GC-MS).

Keywords:

Aniline,

Activated carbon nanoparticles,

Ionic liquid,

Dispersive solid phase extraction

procedure,

gas chromatography–mass

spectrometry

ARTICLE INFO:

Received 10 Aug 2020

Revised form 4 Oct 2020

Accepted 22 Nov 2020

Available online 29 Dec 2020

*Corresponding Author: Saeed Fakhraie

Email: saeedfakhraie@yahoo.com

https://doi.org/10.24200/amecj.v3.i04.126

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

1. Introduction

Aromatic amines such as aniline compounds

are employed as the chemical in industries

(polyurethane foams) and pharmaceutical product.

The reduction of nitrobenzene to aromatic amine

can be occurred without adding of metal (zinc, tin,

or iron) or dihydrogen in polar solvents. Aniline

is an aromatic hydrocarbon and discharge into the

environment through certain industrial efﬂuents

which thereby cause to water contamination [1, 2].

Aniline (C

) with benzene ring and NH

bond can be reacted to other chemicals with sulfur

and carboxyl groups and removed from waters

[3]. The main product of aniline is methylene

diphenyl diisocyanate (MDI) which was used in

polyurethanes as foams in refrigerator insulation.

Aniline use in different industries such as paint,

polymers, pesticides, herbicides, resins, chemicals,

antioxidants, pharmaceuticals, rubber, plastics,

Separation of aniline from waters by MHM-ACNPs Saeed Fakhraie et al

explosives and solvents in perfumes [4]. It should

also be noted that the WHO reported the threshold

for nitrobenzene in water is 30–110 µg L

-1

. EPA

showed, water containing aniline at an average of

6-60 µg L

-1

is not greater than a one-in-a hundred

thousand increased chance of developing cancer.

Aniline is toxic in humans and cause to mutagenic

or carcinogenic effect in the cells of body and DNA

[5]. Aniline cause to myelotoxicity, toxicity of

lymphoid organs and hematopoietic tissues in

human and faunae [6]. Aniline compounds belong

to the blacklist of contaminants material in many

countries. Aniline create the reactive oxygen species

(ROS) and cause to rise lipid hydroperoxide stages,

damage of mitochondrial membrane, damage DNA

and lead to variations in hepatocyte feasibility and

apoptosis [7]. Also, the acute exposure aniline has

toxic reaction in the spleen or liver and cause to

splenomegaly, hyperplasia, brosis, and cancers

with chronic exposure [8]. The toxicity and

carcinogenicity of aniline was reported by NIOSH

and OSHA [9-11]. The acute toxicity of aniline

caused to convert to 4-hydroxyaniline and the

formation of aniline compound with hemoglobin

(Hb). In erythrocytes(RB), this is associated with

the release of iron (Fe) and the accumulation of

methemoglobin (MHb) and the development of

hemolytic anemia and inﬂammation of the spleen.

Tumor formation is often observed in the spleen

on prolonged administration. The International

Agency for Research on Cancer (IARC) classies

aniline as a group 2B carcinogenic compound owed

to its mutagenic and carcinogenic possible [12] and

the concentration of aniline must be evaluated

in water samples. So the removal of aniline

compounds from wastewater is mainly important

for human health and eco-friendly protection. The

analytical techniques include, gas chromatography

[13], Spectroﬂuorimetry [14], the capillary zone

electrophoresis (CZE) with eld-enhanced sample

injection [15,16] and high performance liquid

chromatography (HPLC) [17] were used for the

determination of aniline and derivatives in real

samples. The different method include adsorption,

the biological degradation, the catalytic oxidation

and the electrochemical procedure was used for

eliminating aniline compounds from waters [18-20].

Due to toxicity of aniline and its derivatives, the

aniline value must directly evaluate in water sources.

As low concentration of aniline compounds in

water samples, the pretreatment/preconcentration

of the samples was used before analysis by HPLC,

GC and liquid chromatography-tandem mass

spectrometry [21]. Conventional techniques such

as, adsorption, extraction, the chemical oxidation,

the catalyzed process the electrochemical, the

enzymatic process and the irradiation reported

for anilines separation and determination in water

samples. You et al. developed a new enzymatic

method for the removal of aromatic pollutants from

wastewaters by peroxidases [22, 23]. On the other

hands, adsorbents such as graphene, graphene

oxide, carbon nanotubes, MOF and silica with

different physical and chemical properties were

used for extraction/adsorption anilines from waters.

In this study, the MHM-ACNPs nanoparticles

were used for extraction aniline from waters by

dispersive ionic liquid solid phase extraction

procedure (D-IL-SPE). By procedure, the aniline

adsorbed on nanostructure (MHM-ACNPs-

COO…. NH-C

) at optimized pH. Then, aniline

desorbed from MHM-ACNPs/IL by changing pH

and determined by GC-FID.

2. Experimental

2.1. Apparatus

Agilent Gas chromatography with ﬂame ionization

detector (GC-FID) and mass detector (GC-MS)

based on sample air loop injection (Windows XP

Professional) was used (7890A, Netherland). This

model of GC based on different detectors and

equipped with a split injector was used for aniline

analysis. A Hamilton syringe was used for the

sample injected to the GC injector. The temperature

of the injector tuned for the vaporization of aniline

up to 185-200

C. The temperature of the injector

port and detector of GC was tuned up to 200°C

and 250°C, respectively. The oven temperature

was tune up to 120°C and the ﬂow rate of 1.5 mL

min

-1

for H

was adjusted. The sample liquid was

injected into a GC injector with high temperature

for vaporizing aniline. The liquids samples inject

based on valves to the GC column (0.32 mm ×

0.25 μm). The pressures for inlets and detectors

tuned between 35-100 psi for hydrogen with FID

detector. The GC-MS was used for validation of

aniline results which were adsorbed on MHM-

ACNPs adsorbents. The conditions of GC were

presented in Table 1.

2.2. Reagents

The epoxy resin powders from waste printed

circuit boards (WPCB)

were provided by

Shan- dong Zhonglv Eco-recycle Co. Ltd,

China. According to our previous study

[10], epoxy resin of WPCBs has low

ash content (7%), water ratio (3%), high

volatile matter (67%) and xed carbon

(23%). The carbon was measured by an

energy dispersive spectrometer instrument

(

C: 42.16%). Aniline is an aromatic amine that

may be used as a reactant in the synthesis of

organic intermediates such as pyridine amine,

phenyl amine and phenyl benzamide. So the pure

Aniline prepared (CAS N: 62-53-3) from Sigma

Aldrich. Hydrophobic ionic liquid 1-Butyl-1-

methylpyrrolidinium bis(triﬂuoromethylsulfonyl)

imide (C

, 223437-11-4) with density

of 1.4 g cm

-3

and low solubility in water was used

for collecting of nanoparticles from liquid phase.

Acetone, nitric acid and HCl were purchased from

Merck, Germany. Ultrapure water was obtained

from Millipore Water System (USA), The phosphate

buffer (H

/ HPO

) and ammonium buffer (NH

Cl) prepared from Sigma an used for adjusting

pH between 6.0–8.2 and 8-9, respectively.

2.3. Synthesis of adsorbent

2.3.1.Carbonization

Activated carbons (ACs) was synthesized by

the carbonized method for 2.0 h at 600 °C

by activating at 800 °C for 1 h in a furnace.

The

carbonized chars followed by typically

heats biomass feedstock in a kiln (pyrolysis) at

temperatures between 300-800°C in the absence of

air. The produced also known as charcoal (porous

and carbon-enriched).

The carbonization

furnace was used for the carbonization.

Firstly, 20 g of raw powders prepared and

placed in the porcelain crucible, then heated

up to 600°C per minute and hold for 2.0

hours. By decreasing temperature up to

C, the product is ready for weight [24].

2.3.2.MHM-ACNPs Synthesis

The activation of ACs based on microwave

heating method caused to create

the MHM-

ACNPs by previous works [24-26].

First, the

Table 1. Gas chromatography conditions (Agilent, 7890A)

ValuesParameters

1-10 μLInjection Volume

2:1Split ratio

30 meter, 0.32mm x 0.25μmColumn

200 °CTemperature Injector

250 °CDetector FID

30 to 100 °C @ 25 °C/min,Program

@ 1.5 mL min

-1

Carrier Gas

@ 30 mL min

-1

Gas Makeup

18.1 (min)Retention Time N,N-Dimetnylaniline

10.9 (min)Retention Time Aniline

28 (mL min

-1

)Flow Rate N

60(mL min

-1

)Flow Rate detector H

450(mL min

-1

)Flow Rate air

Anal. Method Environ. Chem. J. 3 (4) (2020) 72-84

carbonized sample was mixed with KOH

(CS/KOH; ratio 1:3; wt/wt). By the simple

heating, the activation of CS/KOH (ACNPs)

was carried out at 800 °C (rate: 25 °C min

; hold: 1h) in a tube furnace and cooling

down to room temperature under N

ﬂow

(0.5 Lmin

-1

). In the microwave heating

method, the

MHM-ACNPs

were achieved by

microwave furnace at a frequency of 2.45

GHz [25]. The mixture of CS/KOH was

placed in

the microwave furnace (800 W)

and heated for 12 min [26]. The product was

cooled up to 25

C under N

ﬂow (0.5 Lmin

). The

MHM-ACNPs

were washed with 10%

HCl and then

washed with DW up to pH=7.

2.4. Extraction procedure for aniline

Due to D-IL-SPE method, the acetone, ionic

liquid and MHM-ACNPs added to 100 mL of

water samples at pH=8. After extraction, the

concentration of aniline determined by GC-FID.

Firstly, 30 mg of MHM-ACNPs added to mixture of

acetone (1 mL) and 1-butyl-1-methylpyrrolidinium

bis(triﬂuoromethylsulfonyl)imide (0.3 g) and then

injected to water and standard solution of aniline

(2.0 µg L

−1

and 950 µg L

−1

). After sonication for

10 min, the benzene ring in aniline as

electron

acceptor

was chemically adsorbed on

carboxylic

groups of MHM-ACNPs

electron donors

(MHM-ACNPs-COO

─

……C

-NH

). The MHM-

ACNPs trapped in 1-Butyl-1-methylpyrrolidinium

bis(triﬂuoromethylsulfonyl)imide and separated

from the liquid phase in the bottom of the conical

tube after centrifuging (3.5 min; 4000 rpm). The

upper of the liquid sample was removed and then,

the aniline back-extracted from MHM-ACNPs

in acidic pH (HNO

, 0.3 mol L

-1

). After shaking

and centrifuging, the remained solution diluted

up to 0.5 mL with DW and determined by GC-

FID (Fig. 1). The procedure was used for a blank

experimental run without any aniline for ten times.

The calibration curve for aniline in standards

solutions was prepared based on D-IL-SPE/GC-FID

procedure (2.0- 950 µg L

−1

) and GC-FID method

(0.4- 800 mg L

−1

) and preconcentration factor (PF)

calculated by curve tting of calibration curves

). Each sample was analyzed separately by

means of a GC-FID. The aniline was detected with

a FID detector. Aniline (mol) were calculated by

the following Equations (1) as extraction efciency

and Equations (2) as recovery,

%EE= [Initial aniline – Final aniline / Initial

aniline] × 100 (1)

%Recovery = Final aniline amount (mol)/ Initial

aniline amount (mol) × 100 (2)

3. Results and Discussion

Fig. 1. The extraction procedure for aniline in waters by MHM-ACNPs and GC-FID

Separation of aniline from waters by MHM-ACNPs Saeed Fakhraie et al

The FTIR showed that the MHM-ACNPs

with high surface area (2792 m

-1

) and

function groups can be efciently absorbed/

extracted the aniline (

-C

) in water

samples as compared to ACs

. For optimizing, the

important parameters on aniline extraction

such as, pH, amount of ionic liquid, sample

volume, amount of sorbent, amount of IL,

shaking time were studied.

3.1. FTIR of MHM-ACNPs

The FTIR spectrum of

MHM-ACNPs

is illustrated

in Figure 2. The band at around 3428 cm

-1

was

attributed to the stretching vibration of hydroxyl.

The 2910 and 2840 cm

-1

bands were respectively

assigned to asymmetric and symmetric C–H

stretching vibration of methylene. The vibration

band at 1710 cm

-1

was identied as C=O stretching

mode of carboxylic groups, while the peak at 1058

-1

was corresponded to the C–O vibration. The

peak at 1613 is characteristic of stretching vibration

of C=C in benzene rings. A group of bands can be

seen between 850 and 500 cm

-1

, which are ascribed

to C-H and CH=CH

vibrations in aromatic rings.

3.2. SEM and TEM of MHM-ACNPs

HR-SEM and HRTEM were used for morphological

study of prepared

MHM-ACNPs

(Fig. 3).

Figure 3a and b illustrates the FE-SEM images

of the synthesized

MHM-ACNPs

sample. The

FE-SEM images of

MHM-ACNPs

sample

displayed small broken pieces of particles with

irregular shapes, which can signicantly affect the

pore characteristics (e.g., pore size distribution

and average pore diameter). From Figure 3b,

MHM-ACNPs

appeared to have many different

sizes of pores, indicating that the structure had

been destroyed and a dense porosity was formed

through KOH activation. In order to observe the

structure of

MHM-ACNPs

anoadsorbents, HR-

500100015002000

2500

300035004000

% Transmitance

Wavenumber (cm

-1

)

O-H

C-H

C=O

C=C

C-O

Fig. 2. The FTIR

spectrum

of MHM-ACNPs adsorbent

Anal. Method Environ. Chem. J. 3 (4) (2020) 72-84

TEM imaging was employed. The HR-TEM image

(Fig. 3c) clearly shows the graphene-like structure

with a 2D morphology, and the image with 50 nm

scale (Fig. 3d) conrms the existence of intermittent

graphitic layers and porous structure.

3.3. Optimizations of parameters for extraction

aniline

The D-IL-SPE procedure based on MHM-ACNPs

nanocomposite was used for extraction of aniline

(NH

-C

) from water and wastewater samples. The

main effectiveness parameters such as, pH, amount

of MHM-ACNPs, amount of ionic liquid, sonication

time, volume of samples, adsorption capacity of

sorbent were evaluated and studied. The mechanism

of adsorption depended on the benzene ring in aniline.

The benzene ring as

electron acceptor

was adsorbed

carboxylic groups of sorbent

electron

donors

(R-COO

─

……C

). After extraction,

the sorbent/aniline was collected by1-butyl-1-

methylpyrrolidinium bis(triﬂuoromethylsulfonyl)

imide as a hydrophobic ionic liquid phase in bottom

of conical centrifuging tube.

3.3.1.

pH effect on aniline extraction

Fig.3. (c)The HR-TEM image of

MHM-ACNPs

by 2D morphology (d) The HR-TEM image of MHM-ACNPs

with intermittent graphitic layers and porous structure

Fig. 3. (a)

the FE-SEM images of the synthesized

MHM-ACNPs (b)

different sizes of pores

Separation of aniline from waters by MHM-ACNPs Saeed Fakhraie et al

The pH sample is critical factor for aniline

extraction in water samples and must be studied.

The efcient extraction of aniline based on MHM-

ACNPs depended on pH value of water samples

which was optimized by D-IL-SPE methods.

The pH range from 2 to 11 was examined with

different buffer solution and the recovery of

aniline extraction in water samples was evaluated

in presence of aniline concentration between

2.0─950 µg L

-1

for 30 mg of MHM-ACNPs. Based

on results, the extraction of aniline was reduced

at acidic pH (pH<6) and pH of 7-9 had more

extraction for aniline in waters (Fig. 4). So, in this

study, the pH of 8.0 was selected as optimized pH

for aniline extraction in waters.

3.3.2.The effect of

MHM-ACNPs adsorbent

on aniline extraction

By proposed method, the amounts of on MHM-

ACNPs adsorbent

for 100 mL of water and

wastewater samples were evaluated. Therefore, the

amount of 5-50 mg of MHM-ACNPs and AC was

used by D-IL-SPE procedure. The results showed

us, aniline efciently extracted by 25 mg MHM-

ACNPs in pH=8. So, the amount of 30 mg of

MHM-ACNPs adsorbent

was selected for aniline

extraction in water samples (Fig. 5).

3.3.3.The effect of

sample volume

on aniline

extraction

The sample volume as an important factor for aniline

extraction in water samples. For this proposed, the

effect of sample volume for extraction of aniline

in waters was evaluated. By procedure, the various

sample volumes between 20-150 mL was used for

optimizing volume in presence of 2.0─950 µg L

-1

aniline concentration for 30 mg of MHM-ACNPs.

The results showed, high recovery obtained for 120

mL of waters. Therefore, 100 mL of sample volume

selected for further studies (Fig. 6).

3.3.4.The adsorption capacity

For evaluating of reusability of MHM-ACNPs,

the nanoparticles of adsorbent were dispersed

in water samples and used for aniline extraction

for many times by the D-IL-SPE procedure. The

experimental results showed, the aniline was

efciently extracted with MHM-ACNPs adsorbent

for 19 cycles of extraction at pH=8.0. So, the MHM-

ACNPs adsorbent can be used for 17 extractions/

back-extraction steps for aniline in waters. The

absorption capacities of adsorbents depended on

the structure, surface area (SA) and nanoparticle

size (NS) in different samples. For calculating of

the absorption capacities, 30 mg of MHM-ACNPs

Fig. 4. The effect of pH on aniline extraction by MHM-ACNPs

and AC adsorbents from water samples

Anal. Method Environ. Chem. J. 3 (4) (2020) 72-84

and AC

nanoparticles

was added to 100 mL of

water samples with 20 mg L

-1

(ppm) of aniline

concentration at pH of 8.0. After 30 min sonication,

the aniline was extracted by MHM-ACNPs and AC

in solutions. Finally, the concentrations of aniline

directly determined in remain solution by GC-FID.

The adsorption capacities of the MHM-ACNPs and

AC structure for aniline were achieved 155.8 mg

-1

and 77.2 mg g

-1

, respectively in water samples.

3.3.5.Aniline validation in real samples

The MHM-ACNPs adsorbent was used for

determination and extraction aniline in water and

wastewater samples. The experimental results

showed, the aniline was efciently extracted with

proposed procedure and validated by spiking of

real samples (Table 2). The validation of the results

were obtained by spiking of water samples with a

standard aniline at pH=8.0.

Fig. 5. The effect of MHM-ACNPs and AC adsorbents

on aniline extraction

by D-IL-SPE method

Fig. 6. The effect of sample volume on aniline extraction

by MHM-ACNPs and AC adsorbents

Separation of aniline from waters by MHM-ACNPs Saeed Fakhraie et al

The extraction efciency of spiked samples

demonstrated that the MHM-ACNPs adsorbent

was satisfactory results for aniline extraction

and determination in in water and wastewater

samples at pH of 8.0. Moreover, the GC-MS were

used for validating of methodology based on

MHM-ACNPs adsorbent and IL by the D-IL-SPE

procedure (Table 3). Also, the aniline extraction

based on MHM-ACNPs adsorbent by the D-IL-

SPE procedure was compared to other adsorbent

and technology which was shown in Table 4.

3.3.6. Discussion

Recently, the aniline was removed/extracted from

different matrixes by various technologies by

researchers. They showed the different adsorbent

and techniques for extraction aniline from

water and wastewater samples and the various

analytical parameters such as, LOD, LOQ, linear

range, RSD% and absorption capacities reported

which was shown in Table 4. Kakavandi et al

were used the Fe

-activated carbon magnetic

nanoparticles (AC-Fe3O4MNPs) for extraction

Table 2. Validation of the D-IL-SPE/GC-FID procedure for determination of aniline in water and wastewater

samples by spiking of standard solutions

Sample Added

(μg L

-1

)

*Found

(μg L

−1

)

Recovery (%)

Tab water ----- 4.24 ± 0.22 -----

5 9.31 ± 0.24 101.4

Drinking water ----- ND -----

10 9.82 ± 0.46 98.2

Well water ----- 19.54 ± 0.95 -----

20 38.98 ± 1.84 97.2

wastewater ----- 335.92 ± 15.11 -----

300 628.33 ± 27.65 97.5

Wastewater ----- 188.60 ± 8.75 -----

200 379.70 ± 16.40 95.6

*x_ ± ts /√n at 95% condence (n=5)

Table 3. Validation of the D-IL-SPE/GC-FID procedure for determination of aniline in water and wastewater

samples by GC-MS

Sample

Added

(μg L

-1

)

GC-MS

(μg L

−1

)

* D-IL-SPE/GC-FID

(μg L

−1

)

Recovery (%)

Water A ----- 11.35 ± 0.28 10.96 ± 0.53 96.6

10 ----- 20.78 ± 0.24 98.2

Water B ----- 53.14 ± 0.57 53.78 ± 2.44 101.2

50 ----- 102.66 ± 4.82 97.8

Water C ----- 98.53 ± 1.67 101.03 ± 5.12 102.5

100 ----- 199.87 ± 9.34 98.8

Water D ----- 202.38 ± 4.12 195.82 ± 10.13 96.8

200 ----- 400.08 ± 18.52 102.1

*x_ ± ts /√n at 95% condence (n=5)

Anal. Method Environ. Chem. J. 3 (4) (2020) 72-84

of aniline in waters and the characterization of

AC-Fe3O4MNPs adsorbent obtained by SEM,

TEM, XRD, and BET [28]. Also, the results were

showed by two kinetic models for adsorption of

AC-Fe3O4MNPs (Langmuir and Freundlich).

The linear range and recovery were achieved 50-

300 mg L

-1

and between 21.1-99%, respectively.

Rahdar et al were presented a novel magnetic

@SiO

nanocomposite (Fe@SiNPs)

for removal aniline from waters by an

electrochemical method. Due to the special

characterization of Fe@SiNPs nanocomposite

such as, vibrating-sample magnetometry

(VSM), XRD, SEM, and FT-IR, the extraction

recovery of 71% was obtained. The physical and

chemical properties of Fe@SiNPs adsorbent

caused to efficient extraction of aniline from

the water samples. By optimizing paramours,

50 mg of Fe@SiNp can be removed aniline in

waters with absorption capacity of 126.6 mg

-1

at pH 6 (50

C) which was lower than the

proposed D-IL-SPE procedure. The adsorption

of aniline by Fe@SiNp is fast and exothermic

which was shown by the kinetic model (r

= 1)

and the Freundlich isotherm model (r

= 0.9986)

[34]. In another study, the polyaniline (PANI)

grafted MWCNTs (PANI/MWCNTs) was used

for extraction of aniline in water samples.

PANI/MWCNTs were characterized by using

ultraviolet−visible spectrophotometry (UV-

VIS), X-ray photoelectron spectroscopy (XFS),

Raman spectroscopy (RS), the differential

thermal analysis (DTA), the differential

scanning calorimetry (DSC), and field-emission

scanning electron microscopy(FE-SEM). The

maximum removal of PANI/MWCNTs adsorbent

was achieved around 99% for aniline in waters

[35]. Based on our study, the MHM-ACNPs were

used for fast, simple and efficient extraction

aniline from waters by dispersive ionic liquid

solid phase extraction procedure (D-IL-SPE). The

aniline adsorbed on nanostructure (MHM-ACNPs

-COO…. C

) with high absorption capacity,

the recovery and the extraction as compared to

other methods. After back-extraction of aniline,

the concentration of aniline is determined by

GC-FID and validated by GC-MS. The wide

working range was obtained from 2.0 to 4000 µg

-1

(RSD% < 1.8) which was higher than other

published methods. Based on Table 4, the LOD,

PF and linear ranges is better than other presented

methods.

Table4. Comparison of proposed procedure with other published methods

Adsorbent Matrix Method Linear range Instrument Recovery

(%)

References

C8-column Water ESI 0.05- 2 µg L

-1

LC- MS/MS 99-102% [27]

AC-Fe3O4MNPs Water Adsorbent 50-300 mg L

-1

XRD,SEM,TEM 21.1-99% [28]

Soybean peroxidase Wastewater Enzymatic ----- UV-Vis 95% [29]

-------- Water NIAA 50–1000 µg L

-1

CZE 93-104% [30]

Activated carbon (AC) Wastewater Enzymatic 20-600 mg L

-1

UV-Vis 89–94% [31]

MFH nanocomposites Wastewater Electrostatic 50-200 mg L

-1

XRD 95.1% [32]

PFPA PAAsW Extraction 0.03–1.4µg L

-1

UHPLC-MS/MS 21–110% [33]

MHM-ACNPs Water Adsorption 2.0-950 µg L

-1

GC-FID/D-IL-SPE 95-102% This work

NIAA: Non-ionic or anionic analytes

CZE: Capillary zone electrophoresis

PFPA: Mobile phases perﬂuoropentanoic acid (PFPA) in water and methanol

PAAsW: Primary aromatic amines (PAAs) in Water

Separation of aniline from waters by MHM-ACNPs Saeed Fakhraie et al

4. Conclusions

In this study, a robust procedure based on MHM-

ACNPs adsorbent was used for the aniline

extraction from water samples. The MHM-

ACNPs/aniline was simply separated/collected

from water samples in bottom of conical tube

by hydrophobic 1-butyl-1-methylpyrrolidinium

bis(triﬂuoromethylsulfonyl) imide. By D-IL-

SPE procedure, the efcient extraction, good

preconcentration, and the prefect sample preparation

was obtained in optimized conditions. By the

mixture of IL/ MHM-ACNPs /acetone, the high

recovery between 95-102% for aniline extraction

were achieved in short time. The developed D-IL-

SPE procedure had many advantages such as, the

favorite reusability, low LOD and RSD% with

accurate and precise results. Therefore, the aniline

can be efciently extracted in water samples based

on MHM-ACNPs adsorbent by D-IL-SPE /GC-

FID procedure.

5. Acknowledgements

The authors wish to thank from Chemistry

Department, Yasouj University, Yasouj, Iran and

Islamic Azad University, Bandar Abbas Branch,

Iran

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