Parisa Paydara and Ali Faghihi Zarandi a,*

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

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

substances, heavy metals are essentially non-

biodegradable and therefore accumulate in the

environment. This contamination poses a risk to

environmental and human health. Some heavy

metals are carcinogenic, mutagenic, teratogenic

and endocrine disruptors while others cause

neurological and behavioral changes especially

in children. Thus remediation of heavy metal

pollution deserves due attention. Different physical

and chemical methods used for this purpose. Heavy

metals enter the environment from natural and

anthropogenic sources [1]. The most significant

natural sources are weathering of minerals,

erosion and volcanic activity while anthropogenic

Air Pollution Method: A new method based on ionic liquid

passed on mesoporous silica nanoparticles for removal of

manganese dust in the workplace air

1. Introduction

Environmental pollution by heavy metals has

become a serious problem in the world. The

mobilization of heavy metals by man through

extraction from ores and processing for different

applications has led to the release of these elements

into the environment. The problem of heavy metals’

pollution is becoming more and more serious with

increasing industrialization and disturbance of

natural biogeochemical cycles. Unlike organic

* Corresponding Author: Ali Faghihi Zarandi

Email: alifaghihi60@yahoo.com

https://doi.org/10.24200/amecj.v2.i01.52

Removal of manganese dust from workplace air; Parisa Paydar & et al

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

Received 15 Dec 2018

Revised form 22 Jan 2019

Accepted 9 Feb 2019

Available online 17 Mar 2019

Keywords:

Manganese dust

Air pollution

Ionic liquid

Mesoporous silica nanoparticles

Solid phase adsorption method

A B S T R A C T

Chronic effect of manganese exposure to humans caused the dysfunction

of nervous system. An applied sorbent based on hydrophobic ionic

liquid passed on mesoporous silica nanoparticles (IL/MSNPs) was

used for adsorption/removal of manganese dust (Mn) from workplace

air by solid phase adsorption method (SPAM). In bench scale set up, 5

mL of standard solution of nitrate and oxide of Mn (0.2-5 mg L-1) was

used for generation of manganese dust in pure air by drying procedure,

and then was passed through column of IL/MSNPs by SKC pump with

flow rate of 200-500 mL min-1 by SKC pump. Moreover, Mn particles

were become absorbed/removal from artificial air by IL/ MSNPs at

80 oC. The Mn particles separated from column of IL/MSNPs by

irrigation of nitric acid solution (2 mL of 0.3 M) before determined by

F-AAS/ET-AAS. In optimized conditions, the adsorption capacity of

MSNPs and IL/MSNPs for Mn removal from air in batch system (1 Li)

was obtained 118.5 mg g-1 and 216.2 mg g-1 respectively. Ultimately,

for validation, spike of Mn particles (bag 1 Li) and ICP was used for

dynamic system.

Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 5-14

6Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)

sources include mining, smelting, electroplating,

use of pesticides, and (phosphate) fertilizers as

well as bio-solids in agriculture, sludge dumping,

industrial discharge, atmospheric deposition etc.

[2]. Examples of essential heavy metals are Fe, Mn,

Cu, Zn, and Ni [3,4]. Non-essential heavy metals

are those, which are not needed by living organisms

for any physiological and biochemical functions.

Examples of nonessential heavy metals are Cd,

Pb, As, Hg, and Cr [5,6]. Blood, urine, and hair are

the most accessible tissues in which to measure an

exposure or dose; they are sometimes referred to

as indicator tissues. Blood and urine concentrations

usually reflect recent exposure and correlate best

with acute effects. In addition, air might be useful

in assessing variations in exposure to metals over

the long term. Manganese is one of the essential

metals for the body. Also, this metal (Mn) is a

required element and a metabolic byproduct of the

contrast agent mangafodipirtrisodium (MnDPDP)

[7]. In addition, exposure to manganese in the

workplace is an occupational health concern, it is

known that even at relatively low levels of exposure

subtle neurological effects have been observed

in workers [8]. Manganese is a transitional metal

and can exist in 11 oxidation states, from 3- to 7+.

The most common valences are 2+, 4+, and 7+. The

most common valence in biological systems is 2+;

moreover, the valence of 4+ is present as MnO2.

Mn+3 is also important in biological systems.

Cycling between Mn+2 and Mn+3 may be potentially

deleterious to biological systems because it can

involve the generation of free radicals. Manganese

is an essential element and is a cofactor for a

number of enzymatic reactions, particularly those

involved in phosphorylation, cholesterol, and fatty

acids synthesis. Manganese is present in all living

organisms [9,10]. The industrial use of manganese

has also expanded in recent years as a ferroalloy

in the iron industry and as a component of alloys

used in welding [11]. Manganese welding is one

of the industries exposed to high concentrations

of manganese. In this process, manganese metal

fumes are produced. According to the NIOSH

standard, the exposure limit for this metal is 0.2 mg

m-3 [12]. The most common form of manganese

toxicity is the result of chronic inhalation of

airborne manganese in mines, steel mills, and

some chemical industries [10]. Industrial toxicity

from inhalation exposure, generally to manganese

dioxide in mining or manufacturing, is of two

types: The first, manganese pneumonitis, is the

result of acute exposure. Men working in plants

with high concentrations of manganese dust show

an incidence of respiratory disease 30 times greater

than normal. Pathologic changes include epithelial

necrosis followed by mononuclear proliferation.

Mn toxicity has been reported through occupational

(e.g. welder) and dietary overexposure and is

evidenced primarily in the central nervous system,

although lung, cardiac, liver, reproductive, and

fetal toxicity have been noted. Mn neurotoxicity

results from an accumulation of the metal in

brain tissue and results in a progressive disorder

of the extrapyramidal system which is similar to

Parkinson’s disease. In order for Mn to distribute

from blood into brain tissue, it must cross either

the blood–brain barrier (BBB) or the blood–

cerebrospinal fluid barrier (BCB). Brain import,

with no evidence of export, would lead to brain

Mn accumulation and neurotoxicity [13,14]. At the

present time, the most commonly used methods

for assessing workplace airborne metal exposures

involve collecting air samples on filters and sending

them to a fixed-site laboratory where a variety of

analytical methods are used. The National Institute

for Occupational Safety and Health (NIOSH) has

developed one quantitative field-portable methods

to measure airborne lead: NIOSH Method 7300,

which uses inductively coupled argon plasma,

atomic emission spectroscopy (ICP-AES) [15,

16]. Also, many analytical techniques have been

employed for the determination of trace levels of

lead in real samples such as, high performance liquid

chromatography coupled to inductively coupled

plasma mass spectrometry (HPLC-ICP-MS)[17],

Inductively coupled plasma mass spectrometry

(ICP-MS)[18], inductively coupled plasma atomic

emission spectrometry (ICP-AES)[19], flame

atomic absorption spectrometry (F-AAS) [20],

Removal of manganese dust from workplace air; Parisa Paydar & et al

electrothermal atomic absorption spectrometry

(ET-AAS)[21], etc. Nowadays, considerable

novel method has been introduced in solid-phase

extraction (SPE) by applying new nanomaterials

with remarkable physicochemical properties

that improve the extraction of analytes. Thus,

many carbonaceous materials such as activated

carbons[22], carbon nanotubes[23], carbon

nanohorns [24], carbon nanocones/disks [25] and

graphene [26- 28] have been applied for analytical

preconcentration due to their unique properties,

such as reduced particle size, big surface area, high

adsorption capacity and good chemical stability

[29]. Porous solids are used technically as adsorbents

catalysts and catalyst supports owing to their high

surface areas. According to the IUPAC definition

[30]. Larger pores are present in porous glasses

and porous gels which were known as mesoporous

materials at the time of the discovery of MCM-

41. With MCM (Mobil Composition of Matter)

41 the first mesoporous solid was synthesized

that showed a regularly ordered pore arrangement

and a very narrow pore-size distribution. After the

discovery of MCM-41 in 1992. This material has

a highly ordered mesoporous hexagonal structure

with mesopore diameters varying from 5 to 30 nm

porous materials are divided into three classes:

pore-size distributions. Other mesoporous solids

microporous (<2 nm), mesoporous (2-50 nm)

and were synthesized via intercalation of layered

mate macroporous (>50 nm). The pore size and

the thickness of the silica walls can be adjusted

by varying the heating temperature and time in

the reaction solution [31]. Careful investigation

of structure of SBA-15 showed that material has

certain amount of micropores which connect

neighboring mesopores [32,33]. The threshold

limit values, permissible exposure limit and

occupational exposure limits (TLV/ PEL/OEL) of

manganese particles exposure in air determined by

international organizations such as, occupational

safety and health administration (OSHA, PEL),

national institute of occupational safety and health

(NIOSH, OEL) and American conference of

governmental industrial hygienists (ACGIH, TLV)

and were 5mg m-3, 3mg m-3, 5mg m-3 respectively

[34].

So, adsorption/ removal of manganese particles

from work place air has more important, due to

the high toxicity in human body. In this study, IL/

MSNPs and MSNPs were used for adsorption/

removal of manganese dust (Mn) from workplace

air by SPAM. The flow rate, mass / type of sorbent,

temperature, and length column are important

parameters which have more effected on removal

efficiency of MSNPs from workplace and artificial

air. The mean of relative standard deviation and

preconcentration factor was less than 5% and 2.5,

respectively.

2. Experimental procedure

2.1. Reagents and instrumental

Determination of manganese was performed with

a spectra GBC flame or electro-thermal atomic

absorption spectrometer (Model, Plus 932, Aus).

A Mn hollow cathode lamp operating at a current

of 5 mA and a wavelength of 279.5 nm with a

spectral bandwidth of 0.2 nm was used. The GBC

demountable torch of inductively coupled plasma

optical emission spectrometer (ICP-OES, Integra

XL, GBC, Aus) with efficient and high performance

at reduced gas flow was used for manganese

determination. The innovative bayonet mount torch

design requires absolutely no re-alignment when

replacing individual components. The Integra’s

standard set of sample introduction components

offer unique capabilities that overcome traditional

limitations. Optical detector based on dual

photomultiplier system (R7154 solar blind tube)

with UV detection was used. The plasma gas with

10 L min-1 (Ar), auxiliary gas with 0.5 L min-1 (Ar),

and nebulizer gas with 0.5 L min-1 (Ar) were used.

The instrumental conditions are shown in Table 1.

All reagents with analytical grade were purchased

from Merck/Sigma (Darmstadt, Germany). Mn

(II) and Mn (V) were prepared by dissolving

appropriate amounts of Mn (NO3)2, MnO, and

KMnO4 in DW. The experimental and working

standard solutions were prepared daily by diluting

the stock solutions with DW. Deionized water

8Analytical Methods in Environmental Chemistry Journal; Vol. 2 (2019)

prepared and simulated in beach scale set up by

standard solution of Mn (Fig. 1). The Mn nitrate

and oxide was generated from 5 mL of standard

solution (0.1 – 5 mg L-1) after drying up to 110

oC by which was mixed with pure air (210 mL of

O2/L; 2.5 mL of H2O /L) at 25 oC. This mixture was

moved to column which was filled with 20 mg of

IL/MSNPs, MSNPs and IL by flow rate of 450 mL

min-1. After adsorption Mn dusts on sorbent, the

column irrigated with 2 mL of nitric acid (0.3 M) and

concentration of Mn in final solution determined

by F-AAS and ICP-OES. Note, the IL paste on

MSNPs caused to increase the adsorption capacity

of Mn dust from air as compared to MSNPs. By

oC, the removal

efficiency was almost increased. The removal

efficiency of proposed method was calculated by

ratio of concentration of Mn in bulk of pilot to

concentration of Mn which was determined by

ICP-OES/F-AAS. For validation of methodology,

different concentration of Mn was generated by

pilot and spike to air samples dust. The recovery

and adsorption capacity (mg g) was calculated

at 50oC as follows: Cs and Cb ( mL-1 or mg L-1)

are concentration in sample and blank solution

respectively. Ci and Cf are the initial and final

concentrations of MnO/Mn(NO3)2. In addition, the

V( mL) and m(mg) were the volume solution and

mass of sorbent, respectively. The recovery was

calculated by using Equation 2.

Eq. 1 Adsorption capacity (mg g) = [(Ci−Cf) V] /m

Eq. 2 Recovey%

100%covRe ×

−

=Ci

)C(C

ery fi

2.4. Characterizations

X-ray diffraction (XRD) patterns were reported

   

radiation (1.54 Å ) operating at 36.5 kV and 30

mA. Diffraction data was recorded between 1 and



-1. Scanning electron micrograph

was recorded using a Zeiss DSM 962 (Zeiss,

Oberkochen, Germany). The sample was deposited

prepared by water purification system (Millipore,

Bedford, MA, USA). Cetylmethyl NH4Br (CTAB),

Na2SiO2 (28 wt % SiO2, 8 wt % Na2O, 64 wt %

H2O), silica gel, C2H5OH, NaOH, HCl and HNO3

all were purchased from Merck, Germany. All

chemicals such as HNO3 and NaOH, acetone were

used as purchased and no further purification was

performed.

2.2. Synthesis

For synthesis, 3.13 grams of CTAB was added to

70.6 g of DW and stirred to change clear. First, 7.8

g of ethanol was added to the surfactant solution

and then, 9.7 g of sodium silicate (28 wt.% SiO2, 5

wt.% Na2O, 65 wt.% H2O) was mixed to surfactant

solution (white suspension). Second, 24.6 g of

sodium carboxyl methyl cellulose solution (12

wt.%) was added to the suspension and stirred for 3

h followed by 2 days aging in oven at 70 oC. Then,

the precipitate of MSNPS was filtered, washed with

deionized water and dried at 100oC overnight. The

MSNPS was placed in a furnace and calcined with

a heating rate of 1 K min-1 to 550oC and held at this

temperature for 6 hours in air. Then, hydrophobic

ionic liquid (HIL) of 1-butyl-3-methylimidazolium

hexafluorophosphate ([BMIM][PF6]) passed on

mesoporous silica nanoparticles (IL/MSNPs). In

addition, 0.4 g of the [BMIM][PF6] with 3 mL

of acetone mixed with 20 mg of MSNPS and after

shaking for 3 min, drying up to 75 oC. MSNPS

modified with IL was made for further study.

2.3. Procedure

The dust of Mn nitrate and oxide in pure air was

Table 1. Instrumental Conditions for Mn determination

by ICP-OES and F-AAS.

ICP-OES F-AAS

Element Mn Mn

Wavelength (nm) 279.48 279.5

Lamp current (mA) -- 5.0

Slit (nm) --- 0.2

Volume spray injection 0.2  per min 2 mL

LOD (µg mL-1) 0.1 0.33

Range a (µg mL-1)0.5-10 

Mode Peak area Peak area

Removal of manganese dust from workplace air; Parisa Paydar & et al

on a sample holder with an adhesive carbon foil

and sputtered with gold. Adsorption/desorption

of Nitrogen was carried out at 77 K using a

BELSORP-mini porosimeter. Prior to analysis the

samples were outgassed in-vacuo for 5 hours at 280

°C until a stable vacuum of 0.12 Pa was reached.

The pore size distribution was calculated from

the desorption branches of isotherms using the

standard BJH procedure and also with geometrical

(pressure independent) method. Transmission

electron microscopy (TEM) was performed on a

LEO Zeiss 912 AB. The morphology of MSNPs

was examined using scanning electron microscopy

(SEM) by Phillips, PW3710, Netherland Company.

Sample were dispersed in ethanol and sonicated

for 30 minutes and deposited on a copper grid. The

synthesis was prepared as the weight of calcined

solid per grams of SiO2 in the initial mixture. The

elemental analyzer (CHNS/O, PerkinElmer, 2400

Series II) was used for determination of elemental

composition of samples. CHN instrument perform

elemental ratio calculations of H/C, N/C, S/C or

C/N.

3. Results and discussion

3.1. SEM and TEM imaging

As shown in Figure 2, IL/MSNPs have a highly

porous morphology and the mesoporous silica

particles are in nanometer range (40-60 nm).

Moreover, IL passed on MSNPs did not led to bulky

silica nanoparticles. TEM image also illustrates

pore structure of IL/MSNPs was shown in figure 5.

Based on TEM, the mesoporous are clearly visible

in the silica nanoparticles and particle size of the

samples is in nanometer range as those observed in

SEM image.

Fig. 1. Beach scale set up with standard solution of Mn by SPAM.

Fig. 2. TEM and SEM of IL/MSNPs sorbent

TEM

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

3.2. Effect of the Mass of MSNPs/IL

The removal efficiency of Mn particles from air

with IL/MSNPs was examined between 5-50 mg.

The results showed, 15 mg of sorbent had more

efficiency for Mn dust removal from air (more than

95%). So, 20 mg of IL/MSNPs was selected as

the optimum amounts of adsorbent in gas phase by

proposed method. Based on results, 20 mg [BMIM]

[PF6] and [EMIM][PF6] and [HMIM][PF6] can be

removal Mn dust from air up to 38.4%, 26%, and

32%, respectively. So, [BMIM][PF6] was used as

IL in this research.

3.3. Removal efciency and Adsorption capacity

In this study, the parameters effected on removal

efficiency and adsorption capacity were studied

OC), flow rates

(50, 100, 200,400 and 600 mL min-1) and initial

concentrations of 0.1-5 mg L-1 (ppm). Finally, the

adsorption capacity of 216.2 mg g-1, 118.5 mg g-1

and 67.4 mg g-1 was obtained for Mn dust removal

from air with 20 mg IL/MSNPs, MSNPs and IL,

respectively. Different ILs such as [BMIM][PF6]

and [EMIM][ PF6] and [HMIM][PF6] passed on

MSNPs and effect of temperature on Mn adsorption

process was investigated. The results showed,

increasing of temperature between 38-70 oC,

decreased the viscosity of ILs and caused to efficient

removal of Mn dust from air, so, 50oC was selected

as optimum temperature. Initial concentrations of

0.01-1 mg L-1 (ppm) of Mn dust were examined

by proposed procedure. It seems that, the initial

concentrations of Mn dusts depended on mass

of sorbent/IL and adsorption capacity. When the

adsorption capacity of IL/MSNPs was increased,

the more concentration of Mn can be used. As a 20

mg of sorbent and adsorption capacity of 216 mg

g-1, the maximum concentration of 4.32 mg of Mn

was obtained.

3.4. Effect of air ow rate

By SPAM procedure, the effect of flow rate for Mn

dust removal from air was studied for 30 samples.

The effect of different flow rates for 20 mg IL/

MSNPs, MSNPs, and IL between 50 to 800 mL

min-1 was tested at room temperature and 50oC. The

flow rate was measured in output of solid phase by

a rotameter. The removal efficiency and adsorption

capacity of IL/MSNPs, MSNPs and IL for Mn dust

were obtained less than 500 mL min-1. So, 450 mL

min-1 was selected as optimum flow rate with IL/

MSNPs phase for removal of Mn dust from air

(Fig. 4).

3.5. Method Validation and Column Condition

The back extraction of Mn from IL/MSNPs was

occurred with the minimal concentration of different

acid solution. By SPAM method, the different acid

solution was used for back extraction Mn ions from

column. Reducing pH, leads to dissociation and

Fig. 2. The effect of concentration for manganese removal from air.

Removal of manganese dust from workplace air; Parisa Paydar & et al

releasing of Mn (II) ions from IL/MSNPs, MSNPs

and IL into acid phase. In order to determine the

type and amount of mineral acidic solution for lead

desorption from IL/MSNPs, different mineral acids

such as HCl, HNO3 and H2SO4 (0.1-1 mol L-1) were

studied by proposed procedure. The results showed,

the 0.3 mol L-1 of HNO3 solution was selected as a

quantitatively acid solution for back extraction of

Mn(II) from IL/MSNPs. By experimental design,

the interaction between manganese dust in air

and IL/MSNPs as a sorbent was evaluated when

the pilot set up correctly. In this method, the IL/

MSNPs, MSNPs and IL was used for removal of

for Mn dust (MnO and Mn(NO3)2) from air by

SPAM. For calculating of accuracy and precision

of dynamic system, the initial Mn concentration in

bench scale set up (bulk container) was determined

by F-AAS and compared to proposed method by

sorbents. By proposed method, the Mn dust with

different concentration from 0.1-1 mg L-1 was

generated and passed through dynamic system

with 450 mL min-1 and removal from air by 20

Fig. 4. Effect of flow rate on recovery percentage.

Fig. 3. The effect of temperature for manganese removal from air.

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

mg of IL/MSNPs. The different concentration of

standard of MnO and Mn(NO3)2 in air bags and

bulk container was determined by F-AAS before

used by proposed method. Since standard reference

material (SRM) for Mn nitrate and oxide in air

dust are not currently available, the spiked of Mn

concentration in air which was generated by bench

-1, 450 mL min-1) were prepared

to demonstrate the reliability of the method by

IL/MSNPs, MSNPs and IL sorbents (Table 2, 3).

For determination of manganese concentration

in lower and upper linear range, the sample was

preconcentration and dilution up to 2.5 and 12.5,

respectively. At optimized set up, more than 98%

of Mn oxide and nitrate in air dust were removed

by IL/MSNPs at 50oC. The high recovery of

spiked samples is satisfactorily reasonable and was

confirmed using addition method, which indicates

the capability of SPAM method for removal of Mn

dust from air. After irrigation of column with 2

mL of nitric acid (0.3 M, pH<4), the Mn ions was

back extracted from IL/MSNPs as a solid phase

and Mn concentration determined by F-AAS. The

validation of methodology was confirmed using

power instrumental analyzer ICP (Table 4).

4. Conclusions

In this research, the adsorption/removal of pollutant

Mn dust from air was achieved based on IL/MSNPs

and MSNPs by SPAM. The results showed, the

unique, efficient, and applied procedure which

was used for removal of Mn particles dust from

workplace and artificial air. For increasing of

removal recovery, Mn concentration, amount of

IL/MSNPs, temperature from 20-100 and flow

rate were studied and optimized. The capacity

adsorption, recovery, removal efficiency of sorbents

was investigated and compared together by F-AAS

and ICP-OES. Based on the results, the adsorption

capacity IL/MSNPs were more than MSNPs for

nitrate/oxide of Mn dust from workplace air. In

addition, the efficiency of adsorption for MnO

Table 2. Method validation for IL/MSNPs by spike of Mn oxide in dust air with F-AAS (mg L-1)

Bench

(Conc.)

Bulk Bench

(Conc.)

Added to bench

(Conc.)

FoundaRecovery (%)

b0.2 0. 16 ± 0.02 0.2 0..31 ± 0.03 96.8

b0.3 0.28 ± 0.02 0.3 0.53 ± 0.05 94.6

b0.5 0.44 ± 0.04 0.5 0.87 ± 0.07 98.9

1.0 0.95 ± 0.08 1.0 1.85 ± 0.11 97.3

c3.0 2.78 ± 0.16 3.0 5.62 ± 0.27 101.2

c5.0 4.69 ±  5.0 9.02±  96.1

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

b (Preconcentration Factor=2.5, Injection volume=2 mL, 450 mL min-1 air flow rate, Peak Area, 20 mg, T=50oC, pH<4)

c (Dilution Factor=2.5, Injection volume=12.5 mL, 450 mL min-1 air flow rate, Peak Area, 20 mg, T=50oC, pH<4)

Table 3. Method validation for IL/MSNPs by spike of Mn nitrate in dust air with F-AAS (mg L-1)

Bench

(Conc.)

Bulk Bench

(Conc.)

Added to bench

(Conc.)

FoundaRecovery (%)

b0.4 0. 35 ± 0.02 0.4 0..67 ± 0.04 95.7

b0.6 0.52 ± 0.05 0.6 0.99 ± 0.10 95.2

1.0 0.92 ± 0.09 1.0 1.88 ± 0.12 102.3

2.0 1.86 ± 0.13 2.0 3.65 ± 0.18 98.1

c3.0 2.65 ± 0.17 3.0 5.18 ± 0.28 97.7

c5.0 4.51 ± 0.25 5.0 8.94± 0.48 99.1

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

b (Preconcentration Factor=2.5, Injection volume=2 mL, 450 mL min-1 air flow rate, Peak Area, 20 mg, T=50oC, pH<4)

c (Dilution Factor=2.5, Injection volume=12.5 mL, 450 mL min-1 air flow rate, Peak Area, 20 mg, T=50oC, pH<4)

Removal of manganese dust from workplace air; Parisa Paydar & et al

and Mn (NO3)2 was increased at more than 38-70

OC and decreased more than 90 oC. Finally, the

results showed that the flow rate is important factor

in dynamic system, and optimized flow rate was

achieved less than 450 mL min-1. The method had

good ability for removal of Mn dust from air.

5. Acknowledgments

We are thankful to Research Institute of Petroleum

Industry (RIPI) and Iranian Petroleum Industry

Health Research Institute (IPIHRI).

6. References

[1] R. A. Wuana, F. E. Okieimen, Heavy metals in

contaminated soils: a review of sources, chemistry,

risks and best available strategies for remediation.

Isrn Ecol., (2011).

[2] H. Ali, E. Khan, M. A. Sajad, Phytoremediation

of heavy metals, concepts and applications,

Chemosphere, 91(2013) 869-881.

[3] E. R. Donati, Heavy Metals in the Environment:

Microorganisms and Bioremediation, CRC Press,

2018.

[4] J.N. Bhakta, Metal toxicity in microorganism.

Handbook of research on inventive bioremediation

techniques. IGI Global, PA, pp.1-23, 2017.

[5] W. Mertz, The essential trace elements. Sci.,

213(1981) 1332-1338.

[6] S. Jena, S. K. Dey, Heavy metals, Am. J. Environ.

Sci., 1(2017) 48-60.

[7] P. Chen, J. Bornhorst, M. Aschner, Manganese

metabolism in humans, Front Biosci., 23(2018)

1655-1679.

[8] M. G. Baker, C. D. Simpson, B. Stover, L. Sheppard,

H. Checkoway, B. A. Racette, N. S. Seixas, Blood

manganese as an exposure biomarker, state of the

evidence, J. Occup. environ. Hgy ., 11 (2014) 210-

217.

[9] J. L. Aschner, M. Aschner, Nutritional aspects of

manganese homeostasis, Mol. Aspects Med .,

26(2005) 353-362.

[10] B. L.Carson, Toxicology biological monitoring of

metals in humans, CRC Press, 2018.

[11] N. H. Mthombeni, S. Mbakop1and, M. S. Onyango,

In adsorptive removal of manganese from industrial

and mining wastewater, proceedings of pustainable

research and innovation conference, (2016) 36-45.

[12] J. Morton, H. Beattie, E. Leese, K. Jones, The

usefulness of biological monitoring in determining

manganese exposure in the workplace, Occup.

Environ. Med., 75(2018).

[13] W. Horst, The physiology of manganese toxicity,

In Manganese in soils and plants, Springer: Com.

Chem., (1988) 175-188.

[14] M. Gawlik, M. B. Gawlik, I. Smaga, M. Filip,

Manganese neurotoxicity and protective effects of

resveratrol and quercetin in preclinical research,

Pharma. Rep ., 69(2017) 322-330.

[15] P. M. Eller, M. E. Cassinelli, NIOSH manual of

analytical methods, Diane Publishing, 94(1994).

[16] J. E. C. Lerner, M. L. Elordi, M. A. Orte, D. Giuliani,

de los Angeles Gutierrez, M.; Sanchez, E.; Sambeth,

J. E.; Porta, A. A., Exposure and risk analysis to

particulate matter, metals, and polycyclic aromatic

hydrocarbon at different workplaces in Argentina,

Table 4. Comparing of different sorbents for removal of Mn oxide by ICP-OES/F-AAS (mg L-1)

Sample* Bulk Bench

(Conc.)

Added

(Conc.)

F-AAS a

(Conc.)

ICP-OES a

(Conc.)

FAAS

Recovery (%)

ICP-OES

Recovery (%)

IL 1.0 ----- 0.26± 0.02 0.29± 0.02 26 29

1.0 0.54± 0.03 0.56± 0.04 28 27

2.0 0.83± 0.04 0.88± 0.05 28.5 29.5

IL/MSNPs 1.0 ----- 0.98± 0.05 0.99± 0.06 98 99

1.0 1.99± 0.09 1.97± 0.10 101 98

2.0 2.96± 0.15 2.95± 0.16 99 98

MSNPs 1.0 ----- 0.52± 0.03 0.56± 0.02 52 56

1.0 1.03± 0.05 1.11± 0.06 51 55

2.0 1.49± 0.07 1.64± 0.08 48.5 54

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

* (450 mL min-1 air flow rate, Peak Area, 20 mg, T=50oC, pH<4)

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

Environ. Sci. Pollut. Res., (2018) 1-10.

[17] N. Solovyev, M. Vinceti, P. Grill, J. Mandrioli, B.

Michalke, Redox speciation of iron, manganese,

and copper in cerebrospinal uid by strong cation

exchange chromatography–sector eld inductively

coupled plasma mass spectrometry, Anal. Chim.

Acta., 973(2017) 25-33.

[18] J. Griboff, D. A. Wunderlin, M. V. Monferran,

Metals, As and Se determination by inductively

coupled plasma-mass spectrometry (ICP-MS)

in edible sh collected from three eutrophic

reservoirs. Their consumption represents a risk for

human health, Microchem. J., 130(2017) 236-244.

[19] A. A. Alqadami, M. Naushad, M. A. Abdalla, M.

R. Khan, Z. A. Alothman, S. M. Wabaidur, A. A.

Ghfar, Determination of heavy metals in skin-

whitening cosmetics using microwave digestion

and inductively coupled plasma atomic emission

spectrometry, IET nanobiotechnol., 11(2017) 597-

603.

[20] M. Baghdadi, F. Shemirani, H. R. L. Z. Zhad,

Determination of cobalt in high-salinity reverse

osmosis concentrates using ame atomic absorption

spectrometry after cold-induced aggregation

microextraction, Anal. Methods, 8(2016) 1908-

1913.

[21] A. Prkić, A. Jurić, J. Giljanović, N. Politeo, V.

Sokol, P. Bošković, M. Brkljača, A. Stipišić, C.

Fernandez, T. Vukušić, Monitoring content of

cadmium, calcium, copper, iron, lead, magnesium

and manganese in tea leaves by electrothermal and

ame atomizer atomic absorption spectrometry,

Open. Chem., 15 (2017) 200-207.

[22] J. LIU, X.f. HU, Gray System Study on the Inuence

of Particle Size Distribution on Adsorption

Performance of Activated Carbon, Bull. Chin.

Ceram. Soc ., 4(2010) 015.

[23] G. G. Wildgoose, C. E. Banks, R. G. Compton,

Metal nanoparticles and related materials supported

on carbon nanotubes: methods and applications,

Small, 2 (2006) 182-193.

[24] M. Roldán-Pijuán, R. Lucena, S. Cárdenas, M.

Valcárcel, Micro-solid phase extraction based

on oxidized single-walled carbon nanohorns

immobilized on a stir borosilicate disk: application

to the preconcentration of the endocrine disruptor

benzophenone, Microchem. J, 115(2014) 87-94.

[25] J. M. Jiménez-Soto, S. Cárdenas, M. Valcárcel,

Evaluation of carbon nanocones/disks as sorbent

material for solid-phase extraction, J. Chromatogr

., 30( 2009) 5626-5633.

[26] I. E. M. Carpio, J. D. Mangadlao, H. N. Nguyen,

R. C. Advincula, D. F. Rodrigues, Graphene oxide

functionalized with ethylenediamine triacetic acid

for heavy metal adsorption and anti-microbial

applications, Carbon, 77(2014) 289-301.

[27] A. Miller, P. L. Drake, P. Hintz, M. Habjan,

Characterizing exposures to airborne metals and

nanoparticle emissions in a renery,. Annal.Occup.

Hyg., 54 (2010) 504-513.

[28] Y. Mao, J. Yuan, J. Zhong, Density functional

calculation of transition metal adatom adsorption

on graphene, J. Phys. Condens. Matter., 20(2008)

115209.

[29] D. R. Dreyer, S. Park, C. W. Bielawski, R. S. Ruoff,

The chemistry of graphene oxide, Chem. Soc. Rev.,

39(2010) 228-240.

[30] M. Oregui-Bengoechea, N. Miletić, W. Hao,; F.

Björnerbäck, M. H. Rosnes,;S. J. Garitaonandia,

N. Hedin, P. L. Arias, T. Barth, High-Performance

Magnetic Activated Carbon from Solid Waste

from Lignin Conversion Processes. 2. Their Use

as NiMo Catalyst Supports for Lignin Conversion,

ACS Sustain. Chem. Eng., 5(2017) 11226-11237.

[31] D. Zhao, J. Feng, Q. Huo, N. Melosh, G. H.

Fredrickson, B. F. Chmelka, G. D. Stucky, Triblock

copolymer syntheses of mesoporous silica with

periodic 50 to 300 angstrom pores, sci., 279(1998)

548-552.

[32] P. Yang, D. Zhao, D. I. Margolese, B. F. Chmelka,

G. D. Stucky, Generalized syntheses of large-pore

mesoporous metal oxides with semicrystalline

frameworks, Nature, 396(1998) 152.

[33] R. Guillet-Nicolas, R. Ahmad, K. A. Cychosz, F.

Kleitz, M. Thommes, Insights into the pore structure

of KIT-6 and SBA-15 ordered mesoporous silica–

recent advances by combining physical adsorption

with mercury porosimetry, New J. Chem., 40(2016)

4351-4360.

[34] K.M. Choi, H.-C. An, Characterization and

exposure measurement for indium oxide nanobers

generated as byproducts in the LED manufacturing

environment. J. Occup. Environ. Hyg., 13(2016)

23-30.

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

Farnaz Hosseinia, Sara Davaria , and Mojtaba Arjomandib,c,*

a Islamic Azad University of Pharmaceutical Sciences (IAUPS), Medical Nano Technology Tehran, Iran

b Department of Water Sciences and Engineering, Science and Research Branch, Islamic Azad University, Tehran, Iran / Research Institute of

Petroleum Industry (RIPI), Tehran, Iran

c Department of Geophysics and Hydrogeology, Geological Survey and Mineral Explorations of Iran (GSI), Tehran, Iran

metal. In addition, aluminum which conveys to

our bodies by having agricultural products and

drinking water accumulates in the tissues of

organs, and after a little time, their functions are

suppressed. Also, a lot of analytical methods

such as weight loss measurements, environmental

scanning electron microscopy, electro-thermal

atomic absorption spectrometry, colorimetric,

kinetic fluorimetric, chelation, and inductively

coupled plasma-mass spectrometry have been

presented by a lot of researchers in the world for

determining the amount of aluminum especially

Al3+ in water, soil, and biological samples. World

A review of constructive analytical methods for determining the

amount of aluminum in environmental and human biological samples

1. Introduction

Aluminum is a toxic metal. This toxic metal

has polluted a lot of water wells, springs, lakes,

groundwater aquifers, rivers, and soil in most parts

of the world. Unfortunately, aluminum accumulates

in plants’ tissues. Also, aluminum foils during

a little time penetrated into food. Nowadays, a

lot of patients who have suffered chronic renal

failure in the world were evaluated. People are

living next to the mines are exposed to this toxic

Corresponding Author: Mojtaba Arjomandi

Email: iranma4@gmail.com

https://doi.org/10.24200/amecj.v2.i01.51

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

Received 28 Dec 2018

Revised form 28 Jan 2019

Accepted 12 Feb 2019

Available online 17 Mar 2019

Keywords:

Analytical and Bioanalytical methods

Aluminum

Human and Environment samples

Toxicity and Measuring.

A B S T R A C T

Aluminum is a toxic metal and cause pollution in soil, water, and

air. Afterwards, a lot of patients suffer renal failure due to the

accumulation of aluminum in the tissues of kidneys. Also, high

concentration of aluminum in plants tissues makes agricultural food

toxic. Therefore, measuring aluminum in water, soil, air, human

organs, tissues of plants and each food (or agricultural product is so

necessary for protecting human healthy. In this paper, the analytical

methods which have been applied for measuring the amount of

aluminum from 1970 to 2019 are focused on. Also, the effect of

some parameters such as pH and temperature on decrease or increase

in the amount of aluminum in water and other samples are stated.

Ultimately, it is worthwhile to mention the analytical methods which

are more time-consuming, cost-effective, applicable, and precise for

determining the amount of aluminum now. In this review, the

analytical methods such as fluorimetric, ICP-MS, colorimetric,

graphite furnace/flame atomic absorption spectrometry, etc. which

have been applied for measuring the amount of aluminum

(especially Al+3) in environmental and human biological samples are

assessed.

A Review of analytical methods for Al in humans; Farnaz Hosseini, et al

Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 15-32

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

health organization (WHO) has studied a lot on the

amount of allowed aluminum in every organ of our

body [1-5]. Wong et al reported about aluminum

and fluoride contents of tea, with emphasis on

brick tea and their health implications [1]. Mameri

et al showed that defluoridation of water by small

plant electrocoagulation using bipolar aluminum

electrodes can be separated many pollutions from

matrix but can be caused aluminum pollutions

in environment [2]. Aluminum and heavy metal

contamination of ground water was evaluated and

determined by Momodu et al. by ET-AAS [3] and

Havas et al. reported analytical method based on

aluminum bioaccumulation in soft water at low pH

[4]. Shaw et al. showed the effect of aluminum in the

central nervous system (CNS) which have caused to

toxicity in humans and animals [5] and Brown et al.

research in analytical method in aluminum species

at mineral surfaces by instrumental analysis [6]. In

1995 -1996, Hodson et al and Neuville et al used

different methods based on for measuring Al in

plants and glasses which was effect in environment

and humans [7,8]. Krewski et al showed Human

health risk assessment for aluminium, aluminium

oxide, and aluminium hydroxide in humans in

2007 [9] and uptake of fluoride, aluminum and

molybdenum by some vegetables from irrigation

water was studied by Khandare et al. at 2006[10].

Occasionally, aluminum was used in different

industry with variety of method which was hazard

effect in humans and environment. For examples,

in 2003, Zn/Al hydrotalcite-like compound

(HTlc) was used for removal of fluoride from

aqueous solution by Das et al [11]. Cosby et al

used a modeling the effects of acid deposition

for extraction of aluminum and Assessment of a

lumped parameter model of soil water and stream

water [12]. Human exposure to aluminum was

evaluated by Niu and Exley [13-15]. Dunemann

et al., showed, simultaneous determination of Hg

(II) and alkylated Hg, Pb, Al and Sn species in

human body fluids using SPME-GC/MS-MS [16].

Messerschmidt et al used adsorptive voltammetry

procedure for the determination of platinum and

aluminum baseline levels in human body fluids

[16] and release of metal ions from dental implant

materials was shown through determination of

Al, Co, Cr, Mo, Ni, V, and Ti in organ tissue by

Lugowski et al [17]. Also, a review paper about

determination of metal-binding proteins by liquid

chromatography was reported by journal of

Analytical and bioanalytical chemistry in 2002

[18]. The concentration of other metals in human

body was evaluated based on different analytical

methods by GC-MS, SPME-CGC-ICPMS, GC‐

MIP‐AED, and anodic stripping voltammetry [19-

26]. Khanhuathon et al used a spectrophotometric

method for determination of aluminum content in

water and beverage samples employing flow-batch

sequential injection system at 2015 [27]. Liu et al

applied Determination of metals in solid samples

by complexation/supercritical fluid extraction

based on gas chromatography and atomic emission

detection for determination metals [28]. Other

methods such as, fluorescence detection and film

microelectrode based on voltammetry was used for

determination metals in body fluids was used [28-

31]. The speciation of aluminum in human serum

was done by Sanz-Medel et al in coordination

chemistry reviews [32]. In 2017, the Nano analysis

in biochemistry for separation of aluminum in

blood of dialysis patients has been developed with

graphene oxide Nanoparticles which have been

dispersed in Ionic Liquid [33].

Moshtaghie et al showed a method for aluminum

determination in serum of dialysis patients by

F-AAS [34]. Halls [35], Bettinelli [36], and Narin

[37] have determined the amount of aluminum

in dialysate fluids and environmental samples

by ET-AAS [34-36]. Aluminum in biological

fluids and dialysis patients was determined with

8-hydroxyquinoline/ extraction/fluorimetry by

Buratti [38] and Davis et al showed a method for

determination of aluminum in human bone [39].

Also, aluminum in biological and water samples

based on cloud point extraction /furnace atomic

absorption spectrometry was developed by Sang

in 2008 [40]. Selvi et al introduce a method

analysis for determination of Aluminum in dialysis

petients by Atomic Absorption Spectrometry by

A Review of analytical methods for aluminum; Farnaz Hosseini, et al

Coprecipitation with LaPO3 in 2017 [41]. Many

methods for determination of aluminum was done

such as lubricating oils emulsified in a sequential

injection analysis system, tri-calcium Phosphate

(TCP), eriochrome cyanine with CPE, dopamine

as an electroactive ligand, by ET-AAS/F-AAS

from 2002 to 2016 [41-45]. The risk assessment of

aluminum based on determination of aluminum in

food/meat was developed by Bassioni and Juhaiman

in 2012 and 2015 respectively [46,47]. Novel

method for determination aluminum in human brain

tissue using lumogallion /fluorescence microscopy

was obtained by Mirza in 2016 [48]. Sorenson et

al. showed that aluminum in the environment and

human samples can be evaluated and Rana Sonia

used Schiff base modified screen printed electrode

for selective determination of Al3+ in different

matrix in 2017 [49,50]. Determination of aluminum

with deep eutectic solvent/microextraction method

was developed in water and food samples in 2018

by Panhwar et al [51] and Lia-yan Liu used by ICP-

AES [52]. Zuziak et al., applied a voltammetry for

determination of aluminum in 2017 [53]. Chao,

Litov and Dórea introduced a analytical method

for breast milk samples [54-56]. In addition, many

analytical method was used for determination and

separation Al from different matrix such as blood

and water samples [57-67]. In this research paper,

it has been tried that the analytical methods which

have been used for quantifying the amount of

aluminum in water, soil, and biological samples

will be assessed. Also, the assessment helps all

scientists and researchers find and use the best

analytical approaches which are more precise and

accurate for determining the amount of aluminum in

the samples. Moreover, this review paper presents

the cost-effective and time-consuming methods

which have been used since 1970 to 2019.

2. Experimental Procedures

2.1. Methodology

In this section, the analytical methods for measuring

aluminum in human body and Environment matrix

were studied. The different metals spread on the

earth’s crust; aluminum (Al) has the third most

abundant element as compared to other metals

with percentage of 88% gram per kilogram. The

free aluminum has never seen in nature and mostly

exists in aluminum silicate minerals and rocks [6-

8]. Aluminum is also exist in different matrixes

such as; air, soil, water, foods and environment.

Based on weathering of metals, the metals enter

to waters and human. Human activity by industrial

processes, waste water effluents and dust as a

major constituent of aluminum compounds can

be released in air, waters, vegetables and human

[9,10].

Many parameters such as coordination chemistry,

pH, and characteristics have effects on behavior of

aluminum in environment [11,12]. In addition, by

biogeochemical cycle of aluminum, geochemical

formations and soil particulates, and air particles

change to aqueous environments and then enter to

soil or sediment. Aluminum is widely was used as

applied metal in all world as a building material.

The different forms of aluminum compounds have

been made by mixing of other elements. In different

pH and conditions, Al can be used with other ions

with different valence states. Aluminum is used

in many fields such as antacids (Al-Mgs), food

additives (Al(OH)3), skin ointment, cosmetics

products, container, and as a metal contaminants

appeared in milk products, juice, fish, and tea

[13-21]. Aluminum also enters in drinking water

due to the water treatment process, weathering

rocks and soils and acid raining. Aluminum is

used in many industries due to special physical

and chemical property. So, aluminum particulates

are seriously exposed by workers of aluminum

factories. The absorption of aluminum in human

body was achieved by many materials such as

citrate, Fe in hem, Ca, F, etc. [21-26]. A precise,

sensitive and selective spectrophotometric

method for determination of Al3+ using (ECR) as

a chromogenic reagent in the presence of N, N

dodecyl trimetylammonium bromide (DTAB)

has been developed by Khanhuathon et al in

2015 [27]. Modern spectrophotometric approach

for determining Al3+ in waters and soft drinks

by using eriochrome cyanine R(ECR) has been

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

presented by Khanhuathon et al. In addition, in

their approach, R(ECR) which is a chromogenic

reagent has been used in the presence of N, N

dodecyl trimetylammoniym bromide (DTAB).

Their study shows that at 584 nm, a maximum

absorption is obtained when pH is equal to 5, Al-

ECR complex is used. In the mentioned study,

the effects of some parameters such as amount

and type of surfactant, pH, and concentration of

EOR on the rate of absorption of Al have been

assessed. Moreover, after optimizing the condition,

a linear range of 0-01 to 0.50mgL-1 aluminum is

received. Also, the range of detection has been

0.0020mgL, and the range of quantification has

been 0.0126mgL. Based on their study, the relative

standard deviation of their approach has been 13%

[28-33]. When the rate of absorption is 0.05 mgL-1,

the applicability of their approach for determining

Al contents is tested on many water samples and

soft drinks. Also, the outcomes of their method

are similar to the ICP-AES method. In addition,

their methods can recovery up to 80%. In addition,

based on their studies, R(ECR) is a suitable

reagent for determining the amount of Al in every

kind of water. Moreover, in their approach, some

cons of using Al-ECR complexes such as time

consuming have been there. In addition, in the

mentioned approach, pH and temperature of the

complexes must be controlled. Also, in the study,

the effects of various surfactants on two properties

of the complexation and reagent, i.e. spectra and

sensitivity, when the pH is equal to 5 have been

considered. The consideration demonstrates the

highest sensitivity of the absorption spectrum

and maximum wavelength which is equal to

584 mm is obtained. Moreover, DTAB (dodecyl

trimetylammonium bromide) is the most effective

surfactant for improving the sensitivity of AL-ECR

[34-42]. Moreover, the study demonstrates that the

maximum absorption is obtained when pH is equal

to 5, as seen in the following figure (Figure 1).

Yildiz et al have studied on determining Al for

tri-calcium phosphate (TCP) anhydrous powder

by flame atomic absorption spectrophotometer in

2016. Based on their study, there is about 350 mg/

kg (w/w) of aluminum in tri-calcium phosphate

anhydrous powder. In the study, the amount of their

metal in the powder is determined using atomic

Fig. 1. Spectra of Al-ECR complexes in the absence (a) and in the presence of various surfactants (b) DTAB, (c)

CTAB, (d) SDS and (e) Triton X-100. Conditions: 0.2 mg L-1 Al, 0.15 mmol L-1 ECR and 3 mmol L-1 surfactant, pH 5.

A Review of analytical methods for aluminum; Farnaz Hosseini, et al

absorption spectrophotometer. In their approach,

the outcomes of Al which have been obtained

by using the N2O-C2A2 flame are similar to the

previous studies. Also, the standard calibration

curve has been done automatically. Moreover, the

accuracy of their method has been considered using

recovery test of aluminum. Finally, their results

show that the amount of Al has been 0.5 mg/kg in

the detection limit and there is a suitable linearity

based on their analysis [43].

Hejri et al has studies on determining trace

aluminum with eriochrome cyanine R after

cloud point extraction in 2011. In their study, for

determining ultra-trace amounts of Al3+ in well

waters, the approach of cloud point extraction

has been used. In addition, during the study, the

surfactant of cetyltrimethylammonium bromid

has been used. Based on their study, linearity has

been ranged from 0.2 ng mgL-1 to 20.0 ng mgL-1.

In their study, the limits of detection is about 0.05

ng mgL-1; moreover, these limits are governed for

determining Al3+, In their method, an interaction

is there between surfactants and metal-dye

complex. Also, in the mentioned method, a ternary

complex which involves surfactant monomers is

formed. Moreover, the efficiency of their method

increases when pH is equal to 5.5. Also, their

results show that by increasing and decreasing

pH, sensitivity will be reduced [44]. In addition,

determining aluminum in biological fluids using

an electroactive ligand, dopamine have been

studied by Bi et al in 2002. Based on their study,

by increasing Al concentration, decreasing trend

of the differential pulse voltammetric anodic peak

is linear. Also, when the experimental conditions

are optimum, two linear ranges which are about 5.0

× 10-8 to 4×10-7 M and 4.0 ×107 to 7.2 × 10-6 M

Al3+ are gained. They have selected some samples

which have been obtained from synthetic renal

dialysate, human whole blood, the urine of patients

who have suffered diabetes. The amount of Al3+

has been measured in the samples using dopamine.

Afterwards, they have verified the depression

electrochemical activities of DA by making a

comparison between electrochemical behaviors

and the spectroscopic responses. In their study,

an indirect method for determining Al3+ with an

electroactive ligand has been applies in biological

fluids using differential pulse voltammetric.

Finally, in the study, a good and suitable agreement

between the results of the study and previous

studies have been made [45]. In addition, Will et al

have considered two methods for determining Al3+

concentrations in blood in 1990. In their study, the

amount of Al which causes chronic renal failure in

patients have been mentioned. In their first method,

plasma samples have been diluted with HNO3/

triton x-100 matric four times. Also, in the second

method, samples are diluted with an equal volume

of Mg (NO3)2 matrix, moreover their samples have

been atomized from a L’vov platform. In addition,

analytical recovery of Al which has been added

to is about 98%. Also, they performed and tested

the samples in sealed containers to maintain them

against contaminations.in the first method, a 10-ml

sample which is the representative of whole blood

has been selected, then centrifuged. Afterwards,

the plasma has been washed by using a disposable

polyethylene pasteur pipet at °C. In their second

method, samples have been diluted in de-ionized

water with the solution of Mg(NO3)2.6H2O which

is 5-46 mmoL/L. Also, for analyzing the samples,

atomic-absorption spectrometric and electrothermal

graphite atomizer with the instruments of model

5100-PE and 5100-PC have been used [46].

Bassini et al have studied on the amount of Al

which causes that food would be contaminated

in 2012. Unfortunately, transferring aluminum

from foil to food is hazardous. In their study, three

techniques such as weight loss measurements,

environmental scanning electron microscopy, and

inductively coupled plasma-mass spectrometry

have been used for analyzing the samples which

have been selected from the foods that exposure to

aluminum foil. The outcomes of their studies show

that in acidic food and cooked food, the amount

of Al is higher in comparison with the other kinds

of foods.in addition, based on their results, the

leaching of Al from foil into food solution as a

solid phase is the same as liquid and vapor phases.

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

Moreover, by increasing temperature, leaching

of Al is increased. Also, when pH decreases, the

rate of leaching rises. Moreover, using aluminum

foil causes a lot of diseases in human body [47].

Al Juhaiman has studied the cons of aluminum

foil which has been wrapped around baking meat

in 2015. Although who has reported the negative

effect of Al foils, unfortunately, a lot of companies

of producing food use it.in their study, the effect

of temperature and cooking time on the amount of

Al which leaches into the food has been assessed.

Based on their results, the leaching of Al in fish

has been the highest, and in chicken, the rate of

leaching of Al has been the lowest. Also, cooking

foods in aluminum pans or other aluminum dishes

increase the rate of leaching. In addition, based on

corrosion weight equation, the rate of Al leaching

in fish, after 60 minutes cooking, is equal to 38.67

mg Al/kg. Also, when this rate is obtained, CR is

about (7.000.71±)×10-3 [48]. In addition, Exley et

al have studied on the accumulation of aluminum

in brain tissue of human in 2016. Based on the

study, when aluminum accumulates in brain

tissue, the human will suffer neuro-degenerative

diseases which include Alzheimer’s disease. Also,

a few studies have been done on visualization of

aluminum. In this study, for measuring aluminum

in brain tissue, transversely heated graphite furnace

with atomic absorption spectrometry has been

used. In their study, fluorescence microscopy and

the flour lumogallion have been developed and

validated for showing the presence of aluminum

in brain tissue. Their research has shown that

fluorescence of aluminum in brain tissue is

different with other metals that accumulate in brain

tissue. Orange fluorescence shows that there is

some aluminum in brain tissue. Their method, i.e.

fluorescence microscopy helps physicians to get

more information about the amount of Al in brain

tissue, and thereby the prevention of being suffered

Alzheimer’s can be followed. Also, Exley et al

have used 4-chloro-3-(2,4 dihydroxyphenylazo)-2-

hydroxybezane-1-sulphonic acid as a lumogallion

for measuring the amount of Al3+ in brain tissue.

Moreover, the lumogallion has been used for

measuring the amount of Al3+ in seawater. When

it is used in seawater, the limit of detection of

CA is equal to 2 Nm. Furthermore, the method

of fluorescence has been used for measuring and

determining the amount of Al3+ in plants. Moreover,

during the test of determination of amount of

Al3+ in the left part of the brain of a patient using

fluorescence microscopy and 1Mm lumogallion,

ph has been equal to 7.4. based on their results, the

concentration of Al3+ in the left part of the brain of

the patient who has suffered alzimer disease ranges

       



orange fluorescence indicates that there is some

aluminum in each tissue. Also, in their study, it is

found out that if pure agarose is spread with Ca2+,

Cu2+, Mg2+, Fe3+ or Zn2+, no fluorescence related to

lumogallion is appeared. Moreover, Exley et al have

found out that the rate of replication of aluminum





et al have been used chromogenic agent with

alizarin reds for determining the amount of trace

aluminum in 2015. Moreover, the determination

of trace aluminum with the agent has been carried

out using ultraviolet spectrophotometer. Also, the

effective parameters on the determination such

as ph, temperature, and reaction time have been

optimized. Their results demonstrates that Fe3+

and Cu2+ have effects on determining Al3+, while

K+ and Na+ have little influence on the mentioned

approach [50-53].

In the procedure, an efficient and new approach

based on graphene oxide nanoparticles (GONPs)

which have been dispersed in ionic liquid (IL) has

been used for in-vitro separation/extraction of trace

Al from the blood of dialysis patients by ultrasound

assisted-dispersive-micro solid phase extraction

    

which have been optimized, the linear range (LR),

limit of detection (LOD), and preconcentration factor

(PF) have been obtained 0.1–4.8 µg L, 0.02 µg L,

and 25 for blood samples respectively (RSD<5%).

The results of blood samples have demonstrated

that the aluminum concentration after dialysis has

A Review of analytical methods for aluminum; Farnaz Hosseini, et al

been higher than before dialysis (128.6±6.7 vs

31.8±1.6, P<0.05). The mean of blood aluminum

has been significantly higher in dialysis patients

in comparison with normal control respectively

(113 5±7.12 vs 1.2±0.1). The developed approach

based on GONPs/IL has been successfully used

for extracting critical level aluminum from human

blood, and the method is suggested for in-vivo

extraction from human body of dialysis patients

after being advocated on an appropriate surface

with biocompatible materials within the human

body. Some other approaches like atomic emission

spectrometry preliminary essay to measure the

amount of biological materials which have been

carried out with existing analytical methods such as

spark or flame atomic emission spectrometry 60-63

with sensitivities approximately 300-3000 less than

ETAAS29 and before many of the contamination

problems associated with sample collection and

preparation were fully appreciated. These methods

have now been largely abandoned but other sources

for atomic emission spectrometry (AES) have

proved successful. A constant-temperature graphite

furnace and measured aluminum in blood and

digested tissues with a detection limit around two-

to fourfold better than ETAAS has been developed

by Baxter et al. Instrumentation for electrothermal

atomization atomic emission spectrometry has

to be constructed by the user; however, some

commercial inductively coupled plasma atomic

emission spectrometry (ICP-AES) systems are

available.

Allainss,M-66 has been used ICP-AES for

measuring aluminum in serum, water, and dialysis

fluids. Although he achieved excellent results, it is

the experience of most workers that the sensitivity

is insufficient to determine normal concentrations

and that time consuming preconcentration steps,

with risks of contamination, are necessary. In the

other papers, the chemical speciation of aluminum

in the low molecular mass (LMM) and high

molecular mass (HMM) fractions of human serum

has been discussed by Alfredo Sanz-Medel et al

[32]. The methodologies, the experimental and

instrumental requirements and the ability of the

reported analytical procedures for identification

of HMM and LMM aluminium species in human

serum are tested in detail. Nonchromatographic

separations coupled to electrothermal atomic

absorption spectrometry for aluminum detection

are compared with chromatographic techniques

(size exclusion chromatography, anion exchange

chromatography, and fast protein liquid

chromatography) coupled to ETAAS or inductively

coupled plasma mass spectrometry (ICP-MS)

detection for Al-HMM species assessments. As

stated before, the complexity of the human serum

samples follows a knowledge and judicious choice

of different principle based separations assisted by

complementary selective detectors. In this vein, a

most advisable first step is the fractionation of the

aluminum biocompounds into two broad groups: (a)

HMM and (b) LMM type of species. This ‘primary’

or ‘rough information’ can provide a constructive

preliminary information. Thus, by using non-

chromatographic approaches, it seems that about

10% of aluminum in human serum is ultrafiltrable

[32-41]; therefore, about 90% of aluminum should

be bound to non-ultrafiltrable HMM proteins. The

query is now which protein(s) binds aluminum

in human serum. In order to reply this query,

chromatographic approaches coupled to Al3+

specific detectors are the most powerful analytical

tools. However, at this stage, a new controversy

arose on the type of chromatography to be applied:

early workers in this field used size exclusion

chromatographic approaches for separating human

serum proteins [37,38-41]. The total concentration

of Al3+ in human serum of healthy subjects which

has been reported by Mothes et al [24] ranges

from 0.5 to 8 mg dm3, while a recent report from

the Sanz-Medel’s group [32] has indicated even

lower normal aluminum concentration (in general

below 0.35 mg dm3) [24]. Due to such very low

concentrations, the speciation of aluminum in

healthy subjects has been possible only in spiked

samples. Most of the investigators have used spiked

serum in such a way that total serum aluminum,

after spiking, ranged between 100 and 200 mg

dm3 matching high concentrations which could

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

be found in the serum of some dialysis patients.

Since reported the concentrations of ultra-filterable

aluminum in serum represented only 10/ 20% of

total aluminum [41], it was necessary to apply very

sensitive analytical procedures in order to identify

and quantify the LMM-Al complexes present even

in spiked serum and in high aluminum level sera

of dialysis patients. Nowadays, there is no doubt

that the analytical approaches for Al3+ speciation

in human serum are needed to appropriately

address the biomedical problems still waiting for

a solution. The vitality of the research work on the

development of new analytical methodologies for

Al speciation in human serum is obvious from the

number of published papers during the last decade.

However, it is obvious that the speciation of Al3+

in biological fluids has been full of problems

with difficulties in the past as is still in a state of

development that has to overcome serious problems

for its extensive application. Although earlier

work seems to have been plugged with serious

contamination problems, some sort of consensus

on the chemical speciation of serum aluminum

has emerged in recent years based on the results of

some work carried out first by ultramicrofiltration,

which demonstrates that usually 90% of total

serum Al3+ is not ultra-filterable (i.e. the metal is

bound to HMM bio compounds). Speciation of

Al3+ in human serum is an extremely difficult task

because the basal levels of this element in serum

are lower than 2 mg/l and these minute amounts are

fractioned in the speciation process. For making

matters worse, the risk of significant exogenous Al

contamination is very high.

In the other study, a reliable determination of

aluminum in serum and aqueous solutions has

been described by Moshtagi-Iie et al. In this

method, using 10% HNO, for glassware and I

mmol EDTA for plastic containers can prevent

the problem of contamination since no delectable

aluminum has been found by making a comparison

between the absorption signals obtained from

fresh sera and water samples with those obtained

from samples held in the containers (data not

shown). The temperature stages used led to the

complete atomization of aluminium and produced

a sensitivity and detection limit of 15 pg, and 2.1

mg.L-1 respectively. Nameless atomic absorption

(Perkin-Elmer 603 spectrophotometer) is used

by Parkinson et al. Moreover, a sensitivity and

detection limit of 35.5 pg and 2.3 mg.L-1 have

been presented by them. Our findings are in good

agreement with their observations. Obviously, the

sensitivity produced by our instrument has been

much betters due to 10 the atomic absorption model

which has been modern. In tile present method, the

linearity of our calibration curve has been up 10.60

ng/mL of aluminum. With such a calibration curve,

we were able to measure aluminum concentrations

in serum, although the serum should be diluted

in higher levels of aluminum. Mazzeo Farinaand

Cerulli has been reported a linearity of up to 50

ng rnL-1 which has been in agreement with our

findings. In the other study, it is found out by Halls

et al that aluminum toxicity has been shown to be a

problem for patients with renal failure on dialysis,

leading, in severe cases, to dialysis dementia, bone

disease, and anemias [35]. The measurement of

aluminum in dialysate fluid can be used to monitor

the exposure of patients on dialysis. The change

in the concentration of aluminum in the fluid

after dialysis can be used to calculate transfer of

aluminum to and from a patient, and to follow the

removal of aluminum with the chelating agent,

desferrioxamine. Moreover, 5 dialysate fluids can

be analyzed by electro-thermal atomic absorption

spectrometry with electro-thermal atomization

(ETAAS-ETA) in the same way as serum. The

object of this work has been to develop a sensitive

and accurate method based on ETAAS-ETA,

which decline the analysis time in accordance with

principles which have been described previously.

In the other methods, a modern chelating resin

based on poly [4-(1-azo-3-hydroxy-4-(N,N-dicarbo

dymethyl) aminophenyl) styrene] for determining

traces level of aluminum and titanium have been

proposed by Basargin et al. For using it in the solid

phase extraction of aluminium, a polystyrene-co-

divinylbenzene) commercial resin (Amberlite XAD-

4) has been modified by grafting onto salicylic acid

A Review of analytical methods for aluminum; Farnaz Hosseini, et al

by Bettinelli et al [36]. Also, a new chelating resin

by fictionalisation of polystyrene–divinylbenzene

with imidazole 4,5-dicarboxylic acid through N=N

bonding for the speciation of vanadium (IV) and

vanadium (V) have been synthesized. Deionized

water is used for preparing all solutions. Otherwise,

stated analytical-grade acids and other chemicals

used in this study have been achieved from Merck,

Darmstadt, Germany. Stock solutions of all metals,

containing 1000 mg (Merck) have been used

for preparation of the standards for the calibration

curve. The calibration standards have never been

submitted to the preconcentration procedure.

The XAD-1180-PV column approach has

been tested with model solutions prior to the

determination of aluminum in the samples. For

the metal determinations, 50 ml of solution which

contains 0.20 g of Al3+ has been added to 10 ml of

buffer solution (the desired pH between 2 and 10).

The column has been preconditioned by passing

buffer solution. The solution has been allowed

to flow through the column under gravity at the

flow rate of 4 ml min. After passing this solution

ending, the column has been rinsed with twice 10

ml of water. The adsorbed metals on the column

have been eluted with 5–10 ml portion of 2 M HCl.

The eluent has been analyzed for determining the

concentration of aluminum by graphite furnace

atomic absorption spectrometer. The characteristics

of XAD-1180-PV chelating resin were prepared.

The thermogravimetric analysis curve of the XAD-

1180- PV chelating resin is shown in three steps. In

the first step, a mass loss of 23% up to 105 C to be

due to adsorbed water on the resin. In the second

step, mass loss is 9.0% up to 340.0 C. In the third

step, mass loss is 34.0% up to 458 C. The mass

losses in the second and third steps are similar to

pyrocatechol violet. There is an agreement between

the situations and the previous studies [24–29].

When the infrared spectra Amberlite XAD-1180

and XAD-1180-PV resins have been compared

with each other, there are additional bands at 1720,

1562, 1374, 1195, and 1120 cm which seem to

originate due to the modification of resin by the

ligand. In addition, there are the characteristics of

C=O, –N=N–, C–OH, –S–O–, and C–N vibrations

respectively.

Moreover, determining trace aluminum in

biological and water samples by cloud point

extraction preconcentration and graphite furnace

atomic absorption spectrometry detection have

been studied by Hongbo Sang et al. In the practical

application of surfactants in analytical chemistry,

separation and preconcentration based on cloud

point extraction (CPE) are becoming vital. The

approach is based on the property of most non-

ionic surfactants in aqueous solutions to form

micelles and to separate into a surfactant-rich

phase of a small volume and a diluted aqueous

phase when heated to a temperature known as

the cloud point temperature. The small volume

of the surfactant-rich phase obtained with this

methodology allows us to design the extraction

schemes which are simple, cheap, highly efficient,

speedy, and lower toxicity to the environment than

those extractions that use organic solvents. Cloud

point extraction has been used for separating and

preconcentrating organic compounds as a step prior

to their determination by liquid chromatography

and capillary electrophoresis. The phase separation

phenomenon has also been used for the extraction

and preconcentration of metal ions after the

formation of sparingly water-soluble complexes.

By research, a TBS-990 atomic absorption

spectrophotometer (Beijing Purkinge General

Instrument Co. Ltd., Beijing, PR China) with a

deuterium background correction and a GF990

graphite furnace atomizer system has been used for

aluminum determination. An aluminum hollow-

cathode lamp has been used as radiation source at

309.3 nm. For CPE, aliquots of 10 mL of a solution

containing the analyte, Triton X-114 and PMBP

buffered at a suitable pH have been kept in the

thermostatic bath maintained at 40 C for 20 min,

and the surfactant-rich phase can settle through

the aqueous phase. The phase separation could

be occur faster by centrifuging for 5 min at 3000

rpm. After cooling in an ice bath, the surfactant-

rich phase became viscous and was retained at the

bottom of the tube. The aqueous phases can readily

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

be discarded simply by inverting the tubes. To

decrease the viscosity of the extract and allow its

pipetting, 200 L of 0.1 mol L−1 HNO3 was added

to the surfactant-rich phase. 20 L of the diluted

extract was introduced into the GFAAS by manual

injection. Calibration has been performed against

aqueous standards which have been submitted to

the same CPE procedure. Ashing and atomization

curves have been established using 10 ng mL−1 Al3+

solutions which have been sent to CPE procedure

and diluted with 10 mL of 0.1 mol L−1 HNO3. In

addition, 20 L of the diluted extract has been used

for GFAAS analysis. The ashing and atomization

curves of Al3+ without CPE procedure were also

studied with 10 ng mL−1 Al3+ in 0.1 mol L−1 HNO3.

By using CPE procedure, the ashing temperature

can be increased by 500 ◦C over the Al3+ solution

without using CPE procedure, and the aluminum

signal has been enhanced twice. There has been

no difference in the shape of the atomization curve

for aluminum with and without CPE procedure,

only the values of absorbance have been different.

In this work, the use of micelle systems as a

separation and pre-concentration for aluminum

offers some advantages including low cost, safety,

preconcentration aluminum with high recoveries

and very good extraction efficiency. The surfactant-

rich phase can be easily introduced into the graphite

furnace after dilution with 0.1 mol L−1 HNO3, and

directly determined by GFAAS. The suggested

method can be applied to the determination of trace

amount of aluminum in various real samples.

As another method, La3+ as releasing agent and

ion suppressor in flame for determining metal

ions has been used by Kılıçkaya Selvia. LaPO4

has been used as co-precipitant for separation and

pre-concentration of heavy metals in several water

samples. Based on our study, LaPO4 has been

firstly used for separation and preconcentration of

aluminum in human dialysis samples. This method

has several advantages such as low detection limit

(LOD), simple, rapid, economic, and precise.

The recoveries of aluminum (III) in the presence

of the most common matrix elements containing

the alkaline and alkaline earth metals were good.

A Perkin-Elmer Analyst A800 Model atomic

absorption spectrometer (Northwalk, USA) with

nitrous oxide/acetylene flame and a D2 lamp

with background corrector was used throughout

the determination of Al3+ in water solutions and

human blood samples. For co-precipitation, 2 µg

aluminum (III), 150 µg lanthanum (III), and 150

µL phosphoric acid (1:2 diluted water) have been

placed in a centrifuge tube. Then the pH of the

solution has been adapted to pH=5 with ammonium

acetate/acetic acid, and the solution has been diluted

to 50 mL with distilled water. After shaking the

solution for several seconds, the solution has been

allowed to stand for 15 min and centrifuged at 3500

rpm for 15 min. The supernatant has been removed

and the precipitate in the tube was dissolved with

0.1 mL of concentrated HNO3 and the volume was

completed to 2 mL with distilled water. The number

of five replicates for each analysis was used. The

water/serum/blood samples were determined by

flame atomic absorption spectrometry.

3. Results and Discussion

Based on some researches which have been

carried out, it is demonstrated that the range of

concentrations of aluminum next to industrial

companies is about 0.4 to 8.0μg/m3 [28-42, 50-53].

Moreover, aluminum concentration in drinking

water ranges from less than < 0.001 to 1.029 mgL-

1[54]. Moreover, the amount of aluminum of milk

of human breast is about 9.2 to 49μgL-1 [55-57].

The concentration of aluminum of soy-based infant

formulas is higher in comparison with milk-based

infant formulas or breast milk [57]. Moreover, the

rate of Aluminum concentration in finished waters

is high due to during the treatment of water, Al3+

is added to water [58]. In addition, it had better be

mentioned that the amount of Al3+ in treated water

is three times more than the water which has not

been treated. Also, the changes of pH and the humic

acid content of the water has effects on the rate of

Al3+ concentrations which have been dissolved.

Also, when pH is less than 5, the concentration of

Al3+ increases. Unfortunately, aluminum particles

have been spread in air, water, and foods, so by

A Review of analytical methods for aluminum; Farnaz Hosseini, et al

inhaling air and having food and water, the rate of

Al3+ increases in body tissues [59-62]. Moreover,

using other consumer items such as antiperspirants,

buffered aspirins, antiulereative medications, and

antiacids causes an increase in the rate of Al3+

in human body. Also, by making a comparison

between aluminum which there is in drinking

water and food, and medicinal preparations which

have Al3+ in themselves, the rate of Al3+ in medical

preparations is much more. The intake or rate of

Al3+ in food ranges from 3.4 to 9 mg/day [63-65].

The amount of Al3+ per tablet/capsule/5 ml dose in

many antiacids is about 104 to 208 mg [66]. The

vegetables and fruit trees which have been grown

using treated water has received more Al3+ in

themselves. It has been found out by Nayak in 2002

that a decrease or increase in Al3+ in human body

does not have any effects on mortality (or mental

health).

People who are living next to the aluminum

companies, plants, and mines, as well as other

hazardous waste sites will suffer chronic kidney

failure. These people or patients must be treated

with phosphate binders and long-term dialysis.

The infants which have been fed soya, antiacids,

and antidiarrheal can be exposed to high levels of

aluminum. Based on TCRI (Toxic chemical release

Inventory), the amount of Aluminum which have

been released from 329 aluminum facilities to the

environment is about 45.6 million pounds [67].

Moreover, total amount of aluminum oxide which

has been released from 59 aluminum processing

companies to air, water, and soil is about 2.9 million

pounds [67].

Table 2-1 list amounts which have been released

from these companies or facilities that they are

grouped by state.

The data which have been obtained by TRI are

Table 1. Releases to the Environment from Facilities that Produce, Process, or Use Aluminum Oxide (fibrous forms)

a Reported amounts released in pounds per yearb Total release

StatecRFdAireWaterfUIgLandhOtheriOn-sitejOff-sitekOff-site

AL 200000000

AR 100000000

CA 100000000

CO 1 0 5 0 480 3 485 3 3

CT 100000000

GA 2 16 175 0 3 0 191 3 3

IA 2 0 0 0 40 0 0 40 40

IL 5 76 0 0 122 23 76 145 145

IN 3 901 250 0 5 10 1 10 1

KY 3 243 0 0 27 0 243 27 27

LA 200000000

MI 2 0 0 0 375 0 0 375 375

a The TRI data should be used with caution since only certain types of facilities are required to report. This is not an exhaustive list.

Data are rounded to nearest whole number.

b Data in TRI are maximum amounts released by each facility.

c

d Number of reporting facilities.

e The sum of fugitive and point source releases are included in releases to air by a given facility.

f Surface water discharges, waste water treatment-(metals only), and publicly owned treatment works (POTWs) (metal and metal

compounds).

g Class I wells, Class II-V wells, and underground injection.

h



i

j The sum of all releases of the chemical to air, land, water, and underground injection wells.

k Total amount of chemical transferred off-site, including to POTWs.

RF = reporting facilities; UI = underground injection

Source: TRI05 2007 (Data are from 2005)

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

not representative of the amount of Al3+ in every

region due to TRI has selected a few facilities. In

addition, inhaling and digesting Al3+ exacerbate

renal failure, bone disease, and anemia. Moreover,

dialysate fluids are made up (in human body) when

aluminium which comes from water supplies is

consumed or used. Unfortunately, human-mades

have changed for ecosystemand increase the

amount of aluminium in the environment. The

element of Al3+ accumulate in plants and water,

and thereby all herbivores are exposed to harmful

effect of aluminium. Also, when a place is polluted

with Al3+, a decrease in the density of populations

is occurred.

Emissions of a lot of Al3+ into water and soil

decreases the fertility. Al3+ as a main factor in acid

soil can limit crop productivity. The interaction

of Al3+ with cell walls can cause the disruption

of the membrane of plasma, and the disruption or

interaction increases when oxidative damage and

mitochondrial dysfunction occur. Also, Al3+ can

damage DNA. When Al3+ accumulates in plants

tissue, DNA starts to be ruined, and after a little

time, it is observed that the rate of the growth of

plants is decreased. In addition, all scientist who

are study on the effects of environmental change on

the plants are rather hesitant and in a dilemma over

whether to adopt the effect of Al3+ on the disruption

of DNA or not. After carrying out a lot of researches,

it has been found out that the accumulation of Al3+ in

tissue of plants cause that DNA with double strand

starts to be broken. In addition aluminum toxicity

depends on the acidity of soil and plant resistance.

Clinical studies show that the patients who have

high concentrations of metals in their brain, bone,

and muscle have unexplained syndrome as dialysis

dementia. Other researches demonstrated that there

are anaemia and ectopic precipitation of calcium in

aluminum toxicity syndrome. Here, some effects of

aluminum on organ of human body are illustrated,

as seen in Figures 2, 3, 4, and 5.

Although by removing dialysis fluid, the rate of Al3+

decreases, in the patients who have suffered renal

failure, the tissue of their body, especially renal

tissues absorbs. More Al3+ in contrast with others;

therefor, in these patients, measuring the amount

of Al3+ in the blood of the patient is indispensable.

Fig. 2. Some disadvantages of aluminum.

Fig. 3. Aluminum’s exposure: A schematic which

explores relationships between exposure,

immediate targets mediating exposure, sinks and

sources of biologically available aluminium with

putative mechanisms of action and finally excretion of

aluminium.

A Review of analytical methods for aluminum; Farnaz Hosseini, et al

of Al3+ in water, human body, and biological

samples. Among the methods which have been used

for measuring the amount of aluminum in water

industry, colorimetric and fluorimetric are common

(widespread) methods which have been used. A

kinetic fluorimetric approach with a claimed limit

of detection of 0.13j.Ig/L-1 using 1.0 ml of serum

has been described by Iannou and piporaki. The

results which have been obtained by flourimetric

method is similar to the results which have been

obtained by electrothermal atomic absorption

spectrometry (ETAAS). For an analysis that more

than 1.0 mL of serum is used, the method of

conventional fluorophore, lumogallion which has

been presented by Suzuki et al is suggested. In the

mentioned methods which have been being used for

measuring the amount of Al3+, the precipitation of

protein, as well making agents occurs. Moreover,

in the two mentioned approaches, pH must be

controlled carefully. Moreover, in colorimetric and

fluorimetric approaches, cationic interferences can

be overcome by masking agents. In addition, the

two methods may be applied for analyzing serum,

but the pros or benefits of the approaches are less

than electrothermal atomic absorption spectrometry

(ETAAS). In the methods, reagents and equipment

which have been required are cheap. The methods

Fig.4. There are 5 major routes by which aluminium

could be transported across cell membranes or cell epi-/

endothelia; (1) paracellular; (2) transcellular; (3) active

transport; (4) channels; (5) adsorptive or receptor-

mediated endocytosis. There are 5 major classes of

forms of aluminium which could participate in these

transport routes. These are shown in the figure as; the

free solvated trivalent cation (Al3+

(aq)); low molecular

weight, neutral, soluble complexes (LMW-Al0

(aq)); high

molecular weight, neutral, soluble complexes

(HMW-Al0

(aq)).

The patients who have suffered chronic renal

failure must be in intravenous therapy, and the rate

of Al in their blood must be measured after each

stage of removing dialysis fluid. Nowadays some

researches about the relation of the amount of Al3+

and dementic mechanisms of intestinal absorption

had better be carried out. Moreover there are a lot of

analytical approaches for determining the amount

Fig. 5. The skin is a sink for topically applied aluminum and will act as a source of biologically reactive aluminum

both to structures within the skin and to the systemic circulation.

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

of colorimetric and fluorimetric can be used for

screening samples which have contamination in

themselves. Also, the approaches are constructive

for analyzing dialysis concentrates.

The procedure of chelation with eight-

hydroxyquinoline when pH is equal to 6 and

isobutyl methyl ketones is extracted into 10 ml

has been suggested by Mazzeo and Lourenzyi

for determining Al3+ in 200 ml of dialysis fluid

concenter by FAAS. A detection limit of 30μg/l

has been obtained. Moreover no interferences from

the high salt content of the concentrates have been

found. Also, after analyzing the samples which

have been dissolved in acid and ashed at 800°C

by FAAS, it has been found out that the migration

of aluminum occurs at the pH which is equal to 2

while the storage is prolonged and temperature is

increasing. Marcin Frankowski et al have used some

approaches such as GF-AAS, ICP-AES, and ICP-

MS to determine the amount of Al3+ in groundwater

samples. Moreover, inorganic aluminum complexes

have been modeled by them. Their studies have

been focused on some ground water samples which

have been selected from the Miocene aquifer

of the city of Poznan, located in Poland. The

amount of Al3+ in the aquifer is variable – from

0.0001 to 725μgL-1. Three analytical methods, i.e.

graphite furnace atomic absorption spectrometry

(GF-AAS), inductively coupled plasma atomic

emission spectrometry (ICP-MS), and Inductively

Coupled Plasma Optical Emission Spectrometry

(ICP-OES) for measuring the amount of aluminum

in the groundwater have been used. The results

which have been obtained from analytical methods

have been have been used to determine the trend

of groundwater from the Mesozoic aquifer to

the Miocene aquifer. Distribution of Al3+ has

been modeled by Frankowski et al in 2011. After

modeling, the existence of aluminum hydroxyl

complexes in some parts of the groundwater has

been confirmed [68]. In addition, based on the

study which has been carried out by Frankowski

et al in 2011, in spite of the fact that sulphates

and organic matter in the most of groundwater

samples are dominant, the aluminum complexes

have never participated in the reaction with the

ligands (based on the modelling) [68]. Also, the

change of the amount of aluminum concentration

in groundwater aquifers due to aluminum’s

amphoteric property causes that founa and flora

will be ruined. Moreover, the low concentration

of aluminum in groundwater aquifer are obtained

when the transformations of aluminosilicates occur

in the active water exchange zone. Soluble complex

bonds with dissolved fluoride (AlF2+, F2

+, AlF3

AlF4

-), Sulphate (AlSO4

+, Al(SO4)2-), phosphate

(AlHPO4

2+, AlHPO4

+) ligands.

With low – molecular organic acids are the major

sources of aluminum in groundwater. In most

aquifers, based on their studies, Al3+ and hydroxide

complexes as exchangeable aluminum fractions are

the main sources of aluminum [68]. Moreover, the

penetration of Al3+, AlOH2+, and Al(OH)2

+into the

agricultural products causes toxicity to humans.

Based on the research which has been carried out

by Frankowski et al in 2011, the high concentrations

of aluminum in groundwater aquifers demonstrate

that hydroxide complexes and organic complexes

are dominant in the aquifers [68]. The concentration

of trace aluminum in groundwater, surface water,

the river have been usually determined by using

GF-ASS (graphite furnace Atomic Absorption

spectrometry). In addition, for measuring the

amount of aluminum in limed lakes, forest soil

waters, and springs, using inductively coupled

plasma mass spectrometry (ICP-MS) is suggested.

Also, for determining the amount of aluminum

in drinking water, inductively coupled plasma

Optical Emission spectrometry (ISP – OES) has

been used. Based on some researches, inductively

coupled plasma mass spectrometry method is

not constructive for determining the amount of

aluminum in water due to the interferences which

have been caused by other elements in water

samples.

4. Conclusions

In this research paper, the importance of measuring

the amount of aluminum complexes in the nature

(soil and water) and human bodies has been paid

A Review of analytical methods for aluminum; Farnaz Hosseini, et al

attention to. Also, some researchers which have

been carried out have been selected and assessed.

All researches have tried to present the best

analytical methods which are more accurate and

precise for determining the amount of aluminum in

water, soil, and biological samples. From 1985 to

2018, the limit of detection has become lower, and

limit of quantification has extended. Nowadays, the

approaches which have been used are more precise,

time-consuming, cost-effective, and applicable.

Also. At the present time, nano-absorbents are used

for separation of Al3+ from blood of human tissues,

water, soil, and plants’ tissues. Between 2016 and

2017, flame atomic absorption spectrometry has

been used to determine the amount of aluminum

in tricalcium phosphate anhydrous powder which

contains about 350mg/Kg-1 aluminum in itself.

From 2011 up to now, for determining the amount

of Al3+ in some top and well water samples, in some

areas of Iran, surfactant cetyltrimethylammonium

bromide and. The method of cloud point extraction

have been used with each other. From 2013

to 2019, for quantifying the amount of Al3+ in

waters and soft drinks of the country of Thailand,

spectrophotometric approach using eriochrom

cyanine has been used. Also, in this method,

the limit of detection is less than 0.0008 and the

limit of detection is about 0.0125 mg/L-1. From,

1982 up to now, for quantifying the amount of

aluminum in human blood, serum, urine, and

tissues, in some European hospital, using electro-

thermal atomic absorption spectrometry has been

suggested. In the decade of 1990, in the hospital

of USA, for determining the amount of aluminum

in blood, the method of diluting plasma samples

with HNO3/Triton X-100, matrix modifier fourfold

was used. Moreover, for measuring the amount of

aluminum in the patients who have suffered less

renal failure, or their renal functions are normal,

diluting samples with an equal volume of Mg

(NO3)2 matrix modifier and atomizing the samples

from a L’vov platform were usual methods. Also,

based on the studies which have been carried out

from 2009 to 2019 about the determination of

aluminum in groundwater aquifers, in most parts

of Eurasia and USA, the concentration of trace

aluminum in groundwater, surface water, and river

have been usually quantified by using GF-ASS

(graphite furnace atomic absorption spectrometry);

moreover, for measuring the amount of aluminum

in limed lakes, forest soil waters, and springs, using

inductively coupled plasma mass spectrometry

(ICP-MS) has rarely been suggested. In addition,

for determining the amount of aluminum in drinking

water, inductively coupled plasma optical emission

spectrometry (ICP-OES) has been used. Also, since

2017 to 2019, in some groundwater aquifers of

London, chemometric methods using optimization

algorithms have been common among a lot of

researchers, scientist, and hydrogeologists for

determining the amount of aluminum. Furthermore,

based on most researches, when pH is more than

7.0, the solubility of aluminum increases, and then

water is polluted. Afterward, lot of people will

suffer renal failure or chronic renal failure.

5. Nomenclatures

CNS: Central Nervous System

CPE: Cloud Point Extraction

ETAAS: Electrothermal Atomic Absorption

Spectrometry

GONPs: Graphene Oxide Nanoparticles

GF-ASS: Graphite Furnace Atomic Absorption

Spectrometry

IL: Ionic liquid

ICP-MS: Inductively Coupled Plasma-Mass

Spectrometry

ICP-OES: Inductively Coupled Plasma Optical

Emission Spectrometry

LR: linear range

LOD: limit of detection

PF: Preconcentration Factor

6. References

1. 1. M.H. Wong, K.F. Fung, H.P Carr, Aluminum and



their health implications, Toxicol. Let., 137 (2003) 111-

120.

2. N. Mameri, H. Lounici, D. Belhocine, H. Grib, D.L.

       

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

small plant electrocoagulation using bipolar aluminum

electrodes, Sep. Purif. Technol., 24 (2001) 113-119.

3. M.A. Momodu, C.A. Anyakora, Heavy metal

contamination of ground water: The Surulere case

study, Res. J. Environ. Earth Sci., 2 (2010) 39-43.

4. M. Havas, Aluminum bioaccumulation and toxicity to

daphnia magna in soft water at low pH, Canadian J.

Fish. Aqu. Sci., 42 (1985) 1741-1748.

5. C.A. Shaw, L. Tomljenovic, Aluminum in the central

nervous system (CNS): toxicity in humans and animals,

vaccine adjuvants, and autoimmunity, Immunol. res.,

56 (2013) 304-316.

6. D.W. Brown, J.D. Hem, Reactions of aqueous

aluminum species at mineral surfaces, Geol. Sur.

Water-Supply Paper, 1975.

7. M.J. Hodson, D.E. Evans, Aluminum/silicon

interactions in higher plants, J. Exp. Bot., 46 (1995)

161-171.

8. D.R. Neuville, B.O. Mysen, Role of aluminum in the

silicate network: In situ, high-temperature study of

glasses and melts on the join SiO2-NaAlO2, Geochim.

Et Cosmochim. Acta, 60 (1996) 1727-1737.

9. D. Krewski, R.A. Yokel, E. Nieboer, D. Borchelt, J.

Cohen, J. Harry, S. Kacew, J. Lindsay, A.M. Mahfouz,

V. Rondeau, Human health risk assessment for

aluminum, aluminum oxide, and aluminum hydroxide,

J. Toxicol. Environ. Health, Part B, 10 (2007) 1-269.

10. A.L. Khandare, G.S. Rao, Uptake of uoride, aluminum

and molybdenum by some vegetables from irrigation

water, J. Human Ecol., 19 (2006) 283-288.

11. D.P. Das, J. Das, K. Parida, Physicochemical

characterization and adsorption behavior of calcined

Zn/Al hydrotalcite-like compound (HTlc) towards

removal of uoride from aqueous solution, J. coll.

interf. Sci., 261 (2003) 213-220.

12. B.J. Cosby, G.M. Hornberger, J.N. Galloway, R.F.

Wright, Modeling the effects of acid deposition:

Assessment of a lumped parameter model of soil water

and stream water chemistry, Water Resour. Res., 21

(1985) 51-63.

13. Q. Niu, Overview of the relationship between aluminum

exposure and health of human being, neurotoxicity of

aluminum, Springer, Singapore (2018) pp.1-31.

14. C. Exley, Human exposure to aluminum. Environ. Sci.,

15 (2013) 1807-16.

15. C. Exley, The toxicity of aluminum in humans. J.

Morphol., 100 (2016) 51-5.

16. L. Dunemann, H. Hajimiragha, J. Begerow,

Simultaneous determination of Hg (II) and alkylated

Hg, Pb, and Sn species in human body uids using

SPME-GC/MS-MS, Fresenius’ j. Anal. Chem., 363

(1999) 466-8.

17. J. Messerschmidt, F. Alt, G. Tölg, J. Angerer, K.H.

Schaller, Adsorptive voltammetric procedure for the

determination of platinum baseline levels in human

body uids, Fresenius’ j. anal. chem., 343 (1992) 391-

18. S.J. Lugowski, D.C. Smith, A.D. McHugh, J.C. Van

Loon, Release of metal ions from dental implant

materials in vivo: determination of Al, Co, Cr, Mo, Ni,

V, and Ti in organ tissue, J. biomed. Mater. Res., 25

(1991) 1443-58.

19. M. de la Calle Guntinas, G. Bordin, A. Rodriguez,

Identication, characterization and determination of

metal-binding proteins by liquid chromatography, A

review. Anal. Bioanal. Chem., 374 (2002) 369-78.

20. J . Boertz, L.M. Hartmann, M. Sulkowski, J.

Hippler, F. Mosel, R.A. Diaz-Bone, K. Michalke,

A.W. Rettenmeier, A.V. Hirner, Determination of

trimethylbismuth in the human body after ingestion of

colloidal bismuth subcitrate, Drug Metab. and Dispos.,

37 (2009) 352-8.

21. A.K. Das, R. Chakraborty, M.L. Cervera, M. De la

Guardia, Determination of thallium in biological

samples, Anal. Bioanal. Chem., 385 (2006) 665-70.

22. M. Guidotti, M. Vitali, Determination of urinary mercury

and methylmercury by solid phase microextraction and

GC/MS, J. High Resolut. Chromatogr., 21 (1998) 665-

23. T. De Smaele, L. Moens, P. Sandra, R. Dams,

Determination of organometallic compounds in surface

water and sediment samples with SPME-CGC-ICPMS,

Microchim. Acta, 130 (1999) 241-51.

24. S. Mothes, R. Wennrich, Solid phase microextraction

and GC-MIP-AED for the speciation analysis

of organomercury compounds, J. High Resolut.

Chromatogr., 22 (1999) 181-2.

25. J. Black, E.C. Maitin, H. Gelman, D.M. Morris, Serum

concentrations of chromium, cobalt and nickel after

total hip replacement: a six month study, Biomater., 4

(1983) 160-4.

26. B. Hoyer, T.M. Florence, Application of polymer-coated

glassy carbon electrodes to the direct determination

of trace metals in body uids by anodic stripping

voltammetry, Anal. Chem., 59 (1987) 2839-42.

27. Y. Khanhuathon, W. Siriangkhawut, P. Chantiratikul, K.

A Review of analytical methods for aluminum; Farnaz Hosseini, et al

Grudpan, Spectrophotometric method for determination

of aluminum content in water and beverage samples

     

Food Compos. Anal., 41 (2015) 45-53.

28. Y. Liu, V. Lopez-Avila, M. Alcaraz, W. F. Beckert,

E. M. Heithmar, Determination of metals in solid



and gas chromatography atomic emission detection, J.

chromatogr. Sci., 31 (1993) 310-6.

29. P. A. Venkateswarlu, Micro method for direct



   

(1975) 277-82.

30. M. Arunyanart, L.C. Love, Determination of drugs in





Appl., 342 (1985) 293-301.

 

     

measurement of trace cobalt and nickel in some

       

acta, 557 (2006) 57-63.

       

Polak, The chemical speciation of aluminum in human

serum, Coordin. Chem. Rev., 228 (2002) 373-83.

33. F. Hosseini, H. Shirkhanloo, N. Motakef Kazemi,

Nano analysis in biochemistry: In Vitro separation and

determination of aluminum in blood of dialysis patients

based on graphene oxide nanoparticles dispersed to

ionic liquid, J. Nanoanal., 4 (2017) 99-109.

34. A.A. Moshtaghie, M. Sandughchin, A. Badil, M. Azani,

development of a method for aluminum determination

       

absorption with graphite furnace, Med. J., 9 (1995)

233-7.

35. D.J. Halls, G.S. Fell, Determination of aluminum in

    

with electrothermal atomization, Analyst, 110 (1985)

243-6.

36. Bettinelli M, Baroni U, Fontana F, Poisetti P. Evaluation



determination of aluminum in serum. Analyst. 110

(1985) 19-22.

37. I. Narin, M. Tuzen, M. Soylak, Aluminum determination

in environmental samples by graphite furnace atomic

absorption spectrometry after solid phase extraction

on Amberlite XAD-1180/pyrocatechol violet chelating

resin, Talanta, 63 (2004) 411-8.

38. M. Buratti, C. Valla, O. Pellegrino, F.M. Rubino,

A. Colombi, Aluminum determination in biological

      



Anal. Biochem., 353 (2006) 63-8

 

measurement of aluminum in human bone: preliminary

human study and improved system performance, J.

Inorg. Biochem., 103 (2009) 1585-90.

40. H. Sang, P. Liang, D. Du, Determination of trace

aluminum in biological and water samples by cloud

point extraction preconcentration and graphite furnace

atomic absorption spectrometry detection, J. Hazard.

Mater., 154 (2008) 1127-32.

        

aluminum in dialysis concentrates by atomic absorption

spectrometry after coprecipitation with lanthanum

phosphate, Iranian j. pharm. Res.. 16 (2017) 1030.

42. J.L. Burguera, M. Burguera, R.E. Antón, J.L. Salager,

M.A. Arandia, C. P, Rondón, Carrero, Y.P. de Peña, R.

Brunetto, M. Gallignani, Determination of aluminum

by electrothermal atomic absorption spectroscopy in

      

analysis system, Talanta, 68 (2005) 179-86.

43. Y. Yildiz, M. Dasgupta, Aluminum determination for

tri-calcium phosphate (TCP) anhydrous powder by

     

(2016) 22-5.

44. O. Hejri, E.B. zorgzadeh, M. Soleimani, R. Mazaheri,

Determination of trace aluminum with eriochrome

cyanine-R after cloud point extraction, World Appl.

Sci. J., 15 (2011) 218-222.

45. F. Zhang, S. Bi, J.Liu, X. Yang, X. Wang, L. Yang, T.

Yu, Y. Chen, L. Dai, T. Yang, Application of dopamine

as an electroactive ligand for the determination of

       

293-299.

46. C.D. Hewitt, K. Winborne, D. Margrey, J.R. Nicholson,

M.G. Savory, J. Savory, M.R. Wills, Critical appraisal

of two methods for determining aluminum in blood

samples, Clin.l chem., 36 (1990) 1466-1469.

47. G. Bassioni, F.S. Mohammed, E. Al Zubaidy, I. Kobrsi,

Risk assessment of using aluminum foil in food

preparation, Int. J. Electrochem. Sci, 7 (2012) 4498-

4509.

48. L.A. Al Juhaiman, Estimating Aluminum Leaching into

Meat Baked with Aluminum Foil Using Gravimetric

and UV-Vis Spectrophotometric Method, Food and

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

Nut. Sci., 6 (2015) 538.

49. A. Mirza, A. King, C. Troakes, C. Exley, The

identication of aluminum in human brain tissue

using lumogallion and uorescence microscopy, J.

Alzheimer’s Disease, 54 (2016) 1333-1338.

50. Sorenson, R.J John, Aluminum in the environment and

human health, Environ. Health Perspect. 8 (1974) 3-95.

51. S. Rana, Schiff base modied screen printed electrode

for selective determination of aluminum (III) at trace

level, Sensor. Actuat. B- Chem., 239 (2017) 17-27.

52. A.H. Panhwar, M. Tuzen, T.G. Kazi. “Deep eutectic

solvent based advance microextraction method for

determination of aluminum in water and food samples:

Multivariate study, Talanta, 178 (2018) 588-593.

53. L. Lia-yan, Determination of aluminum in food of our

by ICP-AES [J], Chinese Journal of Health Laboratory

Technology, 8 (2007).

54. J. Zuziak, M. Jakubowska, Voltammetric determination

of aluminum-Alizarin S complex by renewable silver

amalgam electrode in river and waste waters, J.

Electroanal. Chem., 794 (2017) 49-57.

55. J.G. Dórea, R.C. Marques, Infants’ exposure to

aluminum from vaccines and breast milk during the

rst 6 months, J. Expo. Sci. Environ. Epidemiol., 20

(2010) 598.

56. H.H. Chao, C.H. Guo, C.B. Huang, P.C. Chen, H.C. Li,

D.Y. Hsiung, Y.K. Chou, Arsenic, cadmium, lead, and

aluminum concentrations in human milk at early stages

of lactation, Pediatr. Neonatol., 55 (2014) 127-134.

57. R.E. Litov, V.S. Sickles, G.M. Chan, M.A. Springer,

A. Cordano, Plasma aluminum measurements in term

infants fed human milk or a soy-based infant formula,

J. Pediatric., 84 (1989) 1105-1107.

58. J.E. Van Benschoten, J.K. Edzwald, Measuring

aluminum during water treatment: methodology and

application, J. Am. Water Works Assoc., 82 (1990) 71-

78.

59. A. Bleise, P.R. Danesi, W. Burkart, Properties, use and

health effects of depleted uranium, a general overview,

J. environ. Radioact., 64 ( 2003) 93-112.

60. M.E. Ensminger, A.H. Ensminger, Foods & Nutrition

Encyclopedia, Two volume set, CRC press, 1993.

61. M. W. Holdgate, A perspective of environmental

pollution. CUP Archive, 1980.

62. U. Förstner, G.T. Wittmann, Metal pollution in the

aquatic environment, Springer, Sci. Business Media,

2012.

63. Z. Chen, W. Zheng, L.J. Custer, Q. Dai, X.O. Shu,

F. Jin, A.A. Franke, Usual dietary consumption of

soy foods and its correlation with the excretion rate

of isoavonoids in overnight urine samples among

Chinese women in Shanghai, 1999.

64. H.A. Risch, M. Jain, N.W. Choi, J.G. Fodor, C.J.

Pfeiffer, G.R. Howe, L.W. Harrison, K.J. Craib, A.B.

Miller, Dietary factors and the incidence of cancer of

the stomach. Am. J. Epidemiol., 122 (1985) 947-959.

65. J.M. Llobet, G. Falco, C. Casas, A. Teixido, J.L.

Domingo, Concentrations of arsenic, cadmium,

mercury, and lead in common foods and estimated daily

intake by children, adolescents, adults, and seniors of

Catalonia, Spain, J. Agric. Food Chem., 51 (2003) 838-

842.

66. Zhou, Y. and Yokel, R.A., The chemical species of

aluminum inuences its paracellular ux across and

uptake into Caco-2 cells, a model of gastrointestinal

absorption. Toxicol. Sci., 87 (2005) 15-26.

67. J.A. Hoemer, The Louisiana environmental tax

scorecard, Green Budget Reform: An International

Casebook of Leading Practices, 323, 2014.

68. M. Frankowski, A. Zioła-Frankowska, I. Kurzyca,

K. Novotný, T. Vaculovič, V. Kanický, M. Siepak, J.

Siepak, Determination of aluminum in groundwater

samples by GF-AAS, ICP-AES, ICP-MS and

modelling of inorganic aluminum complexes, Environ.

Monit. Assess., 182 (2011) 71-84.

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

systems, atmospheric deposition is a significant

source of formaldehyde [1], and in drinking water

formaldehyde arises mainly from the oxidation

of natural organic matter during ozonation [2]

and degradation of oxygenates such as methyl

tert-buthyl ether (MTBE) and dimethyl carbonate

(DMC) [3]. It also enters drinking water via

leaching from polyacetal plastic fittings in which

the protective coating has been broken [4].

Formaldehyde is a very toxic compound and has

been classified as a human carcinogen by the

international agency for research on cancer (IARC),

and also as a probable human carcinogen by the

US. Environmental Protection Agency [5].The

Biochemistry Method: Simultaneous determination of formaldehyde

and methyl tert-buthyl ether in water samples using static headspace

gas chromatography mass spectrometry

Ali Akbar Miran Beigia,*, and Mojtaba Shamsipurb

a Oil Rening Research Division, Research Institute of Petroleum Industry (RIPI), Tehran, Iran

b Faculty of Chemistry, Razi University, Kermanshah, Iran

1. Introduction

Formaldehyde (HCHO) is the most widespread

carbonyl compound in the atmosphere. It enters

the environment from natural sources (including

forest fires) and from direct human sources such

as fuel combustion, industrial on-site uses, off

gassing from building materials and consumer

products. Although formaldehyde is a gas at

room temperature, it is readily soluble in water.

Formaldehyde is very active, and is transported

in air, water and contaminated soils. In aqueous

* Corresponding Author: A. A. Miran Beigi

E-mail: amiranbeigi@yahoo.com

https://doi.org/10.24200/amecj.v2.i01.40

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

Received 5 Dec 2018

Revised form 30 Jan 2019

Accepted 15 Feb 2019

Available online 18 Mar 2019

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

Keywords:

Formaldehyde

MTBE

Static headspace-GC/MS

Oil refining

Wastewaters and Water

A B S T R A C T

The present study describes a method based on static

headspace extraction (HS) followed by gas chromatography/

mass spectrometry (GC/MS) for the qualitative and quantitative

analysis of methyl tert-buthyl ether (MTBE) and formaldehyde

(HCHO) in water samples. Cytochrome P4502A6 has important

role for converting of MTBE to tert-butyl alcohol (TBA) and

HCHO. To enhance the extraction capability of the HS, extraction

parameters such as extraction temperature, extraction time, the

ratio of headspace volume to sample volume and sodium chloride

concentration have been optimized. Wide linearity range was

verified in a range of 5-10000 µgL-1 for MTBE (r2=0.9998), while

those for HCHO was 5-500 µg L-1 (r2=0.9996). Detection limits

for MTBE and HCHO was 1.0 µg L-1 and 1.3 µg L-1, respectively.

Best results were obtained when the analyzed oily water samples

were heated to 70 ◦C for 20 min, with the sample volume 10

mL in 20 mL vial, and NaCl 30% (w/v) was used to saturate the

samples. The proposed analytical method was successfully

used for the quantification of analytes in water and wastewater

samples.

Determination of MTBE and HCHO in human; Ali Akbar Miran Beigi, et al

Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 33-42

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

national institute for occupational safety and health

(NIOSH) considered formaldehyde as immediately

dangerous to life and health at 24 mgm-3 (20 µgmL-

1) [6]. It can damage the person’s nerve system, lung

and liver, and cause irritation of eyes, nose, throat

and skin. Therefore, formaldehyde is one of the

analytical interesting substances as a marker of fuel

additive degradation. Its determination becomes

also a hot spot of the research especially in oily

wastewater matrices. A variety of methods for the

determination of formaldehyde have been reported,

including spectrophotometry [7-13], flow-injection

catalytic method [14], high performance liquid

chromatography [15], gas chromatography [16,

17], isotope dilution mass spectrometry [18],

fluorimetry [19, 20], chemiluminescence [21,22],

polarography [23], Fourier Transform Infrared

Absorption [24] and sensors [25-28]. MTBE is also

a volatile organic compound (VOC) produced from

natural gas. It is primarily used for the oxygenation

of fuel to enhance octane number and to improve

the combustion process, in order to reduce

carbon monoxide emissions [29]. MTBE readily

dissolves in water, and moves rapidly through

soils and aquifers. It is resistant to microbial

decomposition and difficult to remove in water

treatment. Its occurrence in the environment is of

a great concern because of the toxicity of MTBE

and its degradation products [30]. Since MTBE is

highly volatile and very soluble in water, it can be

easily found both as airborne pollutants of living

and working environments and as contaminants

of drinking water [31]. To date limited data are

available on the effects of MTBE on health.

Notwithstanding this, USEPA has concluded that at

high doses, MTBE is a potential human carcinogen

and recommended that MTBE levels in drinking

water be kept below a range of 20-40 ppb [32].

MTBE and other oxygenates in ground waters

are frequently measured using standard US EPA

approved methods (e.g., EPA 8021B, EPA 8260B,

ASTM D 4815). These procedures usually perform

gas chromatographic separation coupled with

photo ionization detector (PID), flame ionization

detector (FID) or mass detector (MS). The

introduction of analytes in the chromatographic

apparatus is performed either via direct injection

of water samples (DAI) [33,34], or using sampling

techniques as dynamic headspace (P&T), static

headspace [35], solid phase microextraction

(SPME) [36-44], and solvent microextraction

(SME) [45,46]. The DAI technique presents some

difficulties to be coupled with capillary GC, due to

the large expansion volume of water. Direct water

injections are prone to back flush in the injector

port, which can cause loss of analyte response

as well as injection port contamination. MTBE

oxidation can generate tert-buthyl alcohol (TBA)

and formaldehyde (Fig.1). Our previous study

demonstrated that human cytochrome P450 2A6

is able to metabolize MTBE to tert-butyl alcohol

(TBA) and formaldehyde, a major circulating

metabolite and markers for exposure to MTBE [3].

CYP2A6 plays a significant role in metabolism of

gasoline ethers in liver tissue. The purpose of this

present study is to develop a simple, sensitive and

selective method for simultaneous determination

of trace amounts of formaldehyde and MTBE in

environmental and water samples. To our

knowledge, no method was found in the literature

for this case.

2. Experimental

2.1. Chemicals and Standard Solutions

In this work, analytical grade of chemicals and

reagents were purchased from Merck, Germany.

3HC

CH3

COCH3 3HC C OH

CH3

HCHO

MTBE

Formaldehde

TBA

Fig. 1. MTBE oxidation reaction

Determination of MTBE and HCHO in water; Ali Akbar Miran Beigi, et al

with a heatable CTC agitator for incubation and

shaking, and a robotic arm. To prevent the carry over

 

conditioning of the HS needle and reconditioning

after each analysis. Both the gas station and the



The syringe body was held in the syringe adapter

heater. 20 mL vials sealed with screw top caps

with PTFE/silicon septa were used. Parameters of

the instrument are shown in Table 1. A salt content

of 30 (% w/v) was chosen for the quantitative

determination of target analytes in environmental

and human biological samples.

The GC–MS analysis was performed using a Varian

(CP-3800 series) gas chromatograph equipped

with a mass-selective detector (Varian, quadrupole

1200) and a factor-four, VF-5ms fused-silica

capillary column with a 30m × 0.25 mm i.d. and



conditions were as follows: inlet temperature, 250



The oven temperature was set at 50 C and raised to

C/per min, and raised to 275 C at 20 C



for 1.75 min and the total run time was 20 min.



used as the carrier gas. Mass spectra were obtained

at 70eV in the electron impact ionization mode; the

spectrometer was operated in the full scan mode

over the mass range from 75 to 110(m/z). The

source, transfer line and quadrupole temperatures

were maintained at 200C, 250 C and 200 C,

respectively. Total ion current chromatograms were

acquired and processed using Workstation data

analysis software (Varian). To increase sensitivity,

the selected ion monitoring (SIM) mode was

applied in quantitative analysis. The most abundant

ion was used as the quantified ion. In Table 2, some

Double distilled water (DDW) was used for

preparation and dilution of samples. Helium and

nitrogen (ultrapure carrier grade) were obtained

from Roham gas Company (Tehran, Iran). An

aqueous formaldehyde stock solution, 1000 gm

L, was prepared by diluting 2.5mL of 37%

w/v stock formaldehyde solution (Merck) to 1 L

with deionized distilled water (DDW) and was

standardized by the sulfite method [47]. Working

solutions of formaldehyde were subsequently

prepared by appropriate dilution of the stock

solution with DDW. MTBE Calibration stock

solutions were prepared by adding 10 µL of pure

MTBE (99.5%, Merck) to 10 ml of MeOH (Merck)

in a 10ml vial with a PTFE-silicon septum. The

mixture was manually agitated for 5 min. The

first dilution steps were performed with methanol

whereas further preparation of the standard

solutions was carried out with DDW. The standard

solutions used within 4 weeks. All sample and

standard vials were completely filled to eliminate

headspace. Individual and cumulative working

standard solutions were obtained by appropriate

dilution of the stock in 50 ml of methanol and

further diluted in ultrapure Milli-Q water to prepare

solutions containing MTBE and formaldehyde at

the nanogram per milliliter level. The method was

optimized with MTBE and formaldehyde solutions

of 50 µg/L-1 concentration. It should be noted that in

this work Methyl ethyl ketone (MEK) (50 ng mL-1)

was used as internal standard in environmental

and biological samples.

2.2. Apparatus and Procedure

Static headspace analysis was performed using

a CTC-CombiPAL autosampler (Bender and

Holbein, Zurich, Switzerland) mounted on top of

a GC-MS system. The autosampler was equipped

Table 1. Headspace conditions

Plunger fill speed: 100 µLper secSyringe Temperature : 71ºC

Pre-injection delay: 4 secAgitator Temperature : 70ºC

Plunger injection speed:250 µLper secSample incubation time: 20 min

Syringe flush time:120 secAgitator speed: 500 rpm

sample volume, 10 ml in 22 ml vialAgitation cycle: 2 sec on, 4 sec off

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

analytical conditions of MTBE, formaldehyde and

methyl ethyl keton by GC-MS with SIM mode



were based on the relative peak area of analytes

to the internal standard from the average of three

replicate measurements in environmental and

biological samples.

3. Results and discussion

Various parameters were evaluated during the

method development. In the present study, the

evaluation of individual parameters was carried

out while all other method parameters were kept

constant.

3.1. Extraction temperature

The temperature of sample affects on evaporation

of analyte into the headspace. We expected that

an increase in sample temperature will result in



increased evaporation of the analyte concentration

in the headspace. The effect of sample temperature

was studied by changing the sample temperature

from 40 to 80 C. As can be seen in figure 2, the

amount of extracted analyte (into the headspace)

increases with increasing temperature up to 80 C.

In headspace analysis, it is recommended not to

use high temperatures (in order to avoid the over-

pressurization of the vial sample, and so avoid

accidents) and, therefore, an extraction

temperature of 70C was selected in environmental

and biological samples. The syringe temperature

of 5C above vial temperature was selected to

avoid the analytes condensation.

3.2. Extraction time

The time required for the extraction process was

an important parameter to be investigated. The

most adequate time for the HS extraction was

considered to be the time reaching the equilibrium

of the analytes between the vapor phase and

aqueous phase. Extraction time between 5 and 30

min were tested for the samples of 50 µg L-1 at

70°C

and formaldehyde mixture is shown in figure 3.

An increasing efficiency was observed for both

Table 2. Analytical conditions of MTBE, formaldehyde and methyl ethyl ketone by GC-MS with SIM

method

Quantification ions (m/z)Retention time (min)Molecular weightCompound

301.3930Formaldehyde

731.4588MTBE

431.9073Methyl ethyl keton

Fig. 2. Influence of the extraction temperature on the

relative peak areas of 50 µgL-1 MTBE and formaldehyde

in water.

1750

1770

1790

1810

1830

1850

1870

1890

10000

20000

30000

40000

50000

60000

70000

80000

90000

020 40 60 80 100

Peak area (×1000 counts)

Peak area (counts)

Temperature (oC)

MTBE

HCHO

Fig. 3. Effect of extraction time on peak areas of 50

µgL-1 MTBE and formaldehyde in water at 70 oC.

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

010 20 30 40

Time (min)

Peak area (counts)

830000

850000

870000

890000

910000

930000

950000

970000

Peak area (counts)

HCHO

MTBE

M TBE

HCHO

Determination of MTBE and HCHO in water; Ali Akbar Miran Beigi, et al

compounds when the longer extraction time

was used until 20 min, and then an increase in

extraction time caused a decrease in the efficiency.

A reason for this phenomenon was the transfer of

water molecules to headspace which diluted the gas

phase and decreased extraction amounts. So the

extraction time of 20 min was considered for the

subsequent experiments.

3.3. Ionic strength inuence

Because the ionic strength of the solution

influences the partition coefficient between the

gas and liquid phase (K) the effect of salt amount

on extraction efficiency was also checked. The

effect of the salt on the extraction efficiency was

investigated by comparing the extraction efficiency

of samples which contained different amounts of

sodium chloride (NaCl) from 0 to 40 (%w/v), and

its influence, as the salting out agent, on the ion

abundance of GC-MS chromatogram for MTBE

and formaldehyde is shown in figure 4. As can be

seen the addition of salt does not have the same

effect for both target analytes: the addition of NaCl

led to better results in the case of MTBE, while for

the HCHO no favorable, and sometimes unfavorable

effects (when more than 30% (w/v) of sodium

chloride were employed ) were observed. In human

blood, the effect of different ions on extraction

of Formaldehyde and MTBE based on proposed

procedure was investigated. The interference of

some coexisting ions in water and wastewater

samples on the recovery of Formaldehyde and

MTBE was studied under optimized condition. The

proposed procedure was performed using a 10 mL

sample containing 5-500 µgL-1 of formaldehyde

and MTBE and 2 mg L-1 of different oncentration

of matrix ions such as, Zn2+, Cu2+, Mn2, Na+, K+,

Ca2+ and Mg2+. The tolerate amounts of important

ions and biological matrix (albumin and proteins)

were tested that caused less than 6% of the head

space extraction alteration. In optimized conditions,

the ions and biological matrix do not interfere to

formaldehyde and MTBE extraction by procedure

(less than 5%). The results showed us, the most of

the probable waste matrix concomitant have no

100000

200000

300000

400000

500000

600000

700000

800000

900000

010 20 30 40 50

NaCl content (w/v%)

Peak area (counts)

30000

35000

40000

45000

50000

55000

60000

65000

70000

Peak area (counts)

HCHO

MTBE

M TBE

HCHO

Fig. 4. Effect of NaCl additives on detector

response areas of 50 µgL-1 MTBE and formaldehyde

in water produced by HS for 20 min at 705 oC and

sample volume 10 mL in 20 mL vial

considerable effect on the recovery efficiencies of

formaldehyde and MTBE.

 

increased with increasing concentration of salt in

environmental samples and it reached the peak

yield when NaCl (30%, w/v) was used to saturate

the samples. The reason was considered to be the

increase of ionic strength in aqueous samples by

adding salt, therefore the solubility of analytes

was decreased and more analyte was released into

the headspace. For HCHO the observed behavior

could be explained on account of its high solubility

in water (37%) and strong interaction by solvent

molecules (water) through hydrogen bonding

that cause a greater affinity for water samples.

Therefore, 30 % (w/v) salt content was chosen

for the quantitative simultaneous determination of

both target analytes.

3.4. Sample volume

The ratio of sample volume to headspace volume

is an important parameter that affects the extraction

efficiency of HS. An increase in sample volume and,

consequently, a decrease in headspace volume enhance

the extracted amount of analyte, which improves the

sensitivity. The optimal ratio of the aqueous volume

to the headspace volume for headspace analysis in

20 mL vials was determined by varying the sample

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

volume from 5 mL (1/4 vial volume ) to 15 mL

(3/4 vial volume ). The results are also shown in

Figure 5. The extracted amounts of analytes increase

continuously with increasing sample volume reach a

maximum at an aqueous volume of 10 ml and then

decrease because of the decreased volume of the

headspace. In the work, sample volume of 10.0 mL

(in 20.0 mL vial) was used.

3.5. Evaluation of the method performance

Figure 6 shows a typical total ion chromatogram

(TIC) of a standard solution containing, 100 µg

L-1 of TBE and HCHO after its headspace

extraction under optimal experimental conditions

in wastewater and environmental samples.

The linearity, limits of detection and precision

were calculated when the optimum conditions for

the HS-GC–MS procedure were established. The

linearity of the method was examined by spiking

DDW with MTBE and HCHO in a concentration

range from 5 to 10000 µg L-1 in water samples

and 5 to 500 µg L-1 in biological samples. Each

solution was submitted to the HS-GC-MS

analysis three times. The figures of merit of the

calibration graphs are summarized in Table 3. A

plot of the peak areas against the concentrations of

standards was obtained (Fig.7). Lack-of fit test was

performed to check the goodness of fit and linearity

[48]. Lack-of-fit test demonstrated that the linear

models were adequate because the whole p values

were more than 0.05 at significance level of 95%.

(Table 4).The linear range experiments provided

the necessary information to estimate LODs, based

on the signal that differed three times from the

blank average signal, was 2 and 5 µg L-1 for MTBE

and HCHO, respectively. Analytical accuracy was

assessed from the recovery of analyte spiked to

various of biological and environmental

samples (Table5). The repeatability expressed

as the relative standard deviation (R.S.D.) was

obtained by carrying out five replicate assays on

each water samples (Table 2), and gave a value

less than 4.8% and 2.6% in in biological and

environmental samples, respectively. Therefore,

this method is deemed acceptable for determining

of trace level of µg L-1 in water and

biological matrix.

Fig. 6. Total ion chromatogram (TIC) in SIM mode

of an ultrapure water solution contaminated with

MTBE (50 µgL-1) and formaldehyde (50 µgL-1),

extracted using static headspace. Extraction conditions:

Extraction time: 20 min, Extraction temperature: 70

oC, sample volume 10 mL in 20 mL vial and NaCl

30% (w/v).

10000

20000

30000

40000

50000

60000

0 5 10 15 20

Volume (mL)

Peak area (counts)

745000

750000

755000

760000

765000

770000

775000

780000

Peak area (counts)

MTBE

HCHO

M TBE

Fig. 5. Effect of solution volume in 20 ml vial on

peak areas of 50 µgL-1 MTBE and formaldehyde in

water produced by HS for 20 min at 70 oC.

Determination of MTBE and HCHO in water; Ali Akbar Miran Beigi, et al

Samples 2 and 3 are also the same

synthetic sample 1 that are treated by 20

picomol of human cytochrome P450 (2A6),

prepared from Sigma-Aldrich Co., at 37 oC

for 13 and 30 minutes, respectively.

Cytochrome P450 (2A6) is known as one of the

most effective enzymes in metabolism

alkoxyethers. In order to control enzyme

activity and termination of reaction time, it was

need to a deactivator such as 100 µl of 0.10 M

perchloric acid. Formaldehyde was also a mainly

byproduct of enzymatic degradation reaction of

MTBE and was detected by developed method as

given in Table 6. In the case of formaldehyde,

although the calculated values can be estimated

stoichiometrically.

Fig. 7. Standard calibration curves of peak areas against the concentrations of MTBE () and HCHO (). MTBE:

y = 14.90x + 28.32 (r = 0.996), HCHO: y = 61.07x + 88.88 (r = 0.998).

Table 3. Analytical figures of merit of the determination of MTBE and HCHO (µg L-1)

Compound Regression Equation a Linear Range LOD

RSD

(%, n = 5)

0.1 40

MTBE y =513.24x+0.319 5-10000 2 4.8 6.8

formaldehyde y = 1.759x + 27.53 5-500 5 1.9 7.8

a y: Analyte area-to-internal standard area, x: concentration (µg L-1).

3.6.Analysis

The proposed method was firstly used to quantify

MTBE and HCHO in wastewaters related with

Tehran oil refinery and human blood and urine

of petrochemical workers. The obtained results in

Table 5, were showed good recoveries, and the

method was ideally suited for these matrices.

The synthetic biological samples were also

analyzed by the develop method (Table 6). Here,

blank is containing 500 µl mixture of 50 mM tris-

HCl buffer (pH=7.4), 1mM NADPH (as inducer),

10 mM MgCl2 and 150 mM KCl (as electrolytes).

Synthetic sample 1 is prepared by addition of 5.02

µg ml-1 MTBE in the blank solution.

Table 4. 

Compound Correlation coefﬁcient, r Determination coefﬁcient, R2Lack-of-fit, pa

MTBE 0.9998 0.9993 0.089 > 0.05

Formaldehyde 0.9996 0.9984 0.078 > 0.05

a Confidence interval, 95%.

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

5. References

[1] R.J. Kieber, M.F. Rhines, J.D. Willey, Rainwater

formaldehyde: concentration, deposition and

photochemical formation, Atmos. Environ., 33 (1999)

3659-3667.

[2] J. K. Fawell, Formaldehyde in Drinking-water,

Background document for development of Guidelines

for drinking-water quality, World Health Organization

(WHO), UK, 2005.

[3] M. Shamsipur, A. A. Miran Beigi, M. Teymouri,

T. Poursaberi, S.M. Mostafavi, P. Soleimani,

Biotransformation of methyl tert-butyl ether by

human cytochrome P450 2A6, Biodegradation, 23

(2012) 311-318.

[4] R.G. Liteplo, R. Beauchamp, M. E. Meek, R. Chenier,

Concise international chemical assessment document

40: formaldehyde, World Health Organization

(WHO), Geneva, 2018.

[5] U.S. Environmental Protection Agency (USEPA),

report to congress on indoor air quality, assessment

and control of indoor air pollution, Volume 2, 2017.

[6] National Institute for Occupational Safety and Health

(NIOSH), Manual of analytical methods, 4th ed.,

department of health and human services, Cincinnati,

OH, USA, 2018.

[7] G. Nael, Y. H. S. Maha, A. Mosallb, Spectrophotometric

determination of formaldehyde based on the

Table 5. Determination of HCHO and MTBE in water and Human samples at optimum extraction conditions (µg L-1)

Well water c

Tap water

Water Recovery (%)Found

aAddedConc.Recovery (%)Found

aAddedConc.

95.623.9 ± 4.225.0NDb

100.825.2 ± 2.825.0NDb

HCHO

97.036.2 ± 3.125.012.097.624.4 ± 4.825.0NDb

MTBE

PetrochemicalOil company

Wastewater

Recovery (%)Found

aAddedConc.Recovery (%)Found

aAddedConc.

97.022.5 ± 4.210.012.896.541.4 ± 2.320.022.1HCHO

96.019.3 ± 3.110.09.7103.136.9 ± 1.520.016.3MTBE

a Mean of triplicates with percent R.S.D (n=5).

b Not found.

c Well water nearby Tehran oil refinery.

standard method based on derivatization with 2,

4-dinitrophenylhydrazine and HPLC detection was

used to assay the values[49]. An average recovery

of 65.5 and 91.7 % was obtained for degradation

process of MTBE after passing 13 and 30 min. from

course of the reaction, respectively. The standard

deviation of measurements at ppm levels was not

greater than 2.6%.

4. Conclusions

An automated and simple method has been

developed for simultaneous determination of MTBE

and formaldehyde in water and human matrices.

It was based on the use of HS device coupled

with a GC–MS instrument. The no necessity of

consumables or reagents for sample treatment made

HS-GC–MS to be considered as the best extraction

option of the studied ones. The analysis required

20 min of sample incubation or extraction time and

less than 5 min for chromatographic determination

programming the MS detector in SIM acquisition

mode. Good precision and the simple sample

preparation enable to use this procedure for

routine investigations. This proposed method was

applied to the analysis in water samples.

telomerization reaction of tryptamine, Arabian J.

Table 6. Simultaneous determination of MTBE and Formaldehyde in synthetic biological samples

Formaldehyde / µgml-1

MTBE / µg ml-1

SampleNo.

FoundCalcd.FoundCalcd.

--4.915.02Synthetic sample 11

1.141.091.73-Synthetic sample 22

1.531.480.415-Synthetic sample 33

Determination of MTBE and HCHO in water; Ali Akbar Miran Beigi, et al

Chem., 8 (2015) 487-494.

[8] N. Jaman, Md. S. Hoque, S.C. Chakraborty, Md. E.

Hoq, H.P. Seal, Determination of formaldehyde

content by spectrophotometric method in some fresh

water and marine shes of Bangladesh, Int. J. Fish.

Aqu. Studies 2 (2015) 94-98.

[9] L. Bolognesi, E. J. dos Santos, G. Abate, Determination

of formaldehyde by ow injection analysis with

spectrophotometric detection exploiting brilliant

green–sulphite reaction, Chem. Papers, 69 (2015)

791–798.

[10] N. Teshima, S. K. M. Fernández, M. Ueda, H.

Nakai, T. Sakai, Flow injection spectrophotometric

determination of formaldehyde based on its

condensation with hydroxylamine and subsequent

redox reaction with iron(III)-ferrozine complex

Talanta, 84 (2010) 1205-1208.

[11] A. Afkhami, H. Bagheri, Preconcentration of trace

amounts of formaldehyde from water, biological

and food samples using an efcient nanosized solid

phase, and its determination by a novel kinetic

method Microchim. Acta, 176 (2012) 217-227.

[12] A. Blondel, H. Plaisance, Screening of formaldehyde

indoor sources and quantication of their emission

using a passive sampler, Build. Environ., 46 (2011)

1284-1291.

[13] S. Abbasi, M. Esfandyarpour, M. A. Taher, A.

Daneshfar, Catalytic-kinetic determination of trace

amount of formaldehyde by the spectrophotometric

method with a bromate-Janus green system,

Spectrochim. Acta, 67 (2007) 578-581.

[14] Zh.Q. Zhang, H.T. Yan, X.F. Yue, Catalytic

determination of trace formaldehyde with a ow

injection system using the indicator reaction between

crystal violet and bromate, Microchim. Acta, 146

(2004) 259-263.

[15] M.K.L. Bicking, W.M. Cooke, F.K. Kawahara, J.E.

Longbottom, The effect of pH on the reaction of

2,4-Dinitrophenylhydrazine with formaldehyde and

acetaldehyde, J. Chromatogr., 455 (1988) 310-314.

[16] X.Y. Sui, X.M. Li, Z.Y. Zhang, Y. Song, L. Chen, H.Zh.

Zhang, Analysis of free formaldehyde in textiles by

gas chromatography, Chin. J. Anal. Chem. 30 (2002)

1333-1336.

[17] L. Nondek, R.E. Milofsky, J.W. Birks, Determination

of carbonyl compounds in air by HPLC using on-

Line analyzed microcartridges, uorescence and

chemiluminescence detection, Chromatographia, 32

(1991) 33-39.

[18] R.T. Rivero, V.J. Topiwala, Volatile organic

compounds(VOCs) in marine water at the ng

concentration level, J. Chromatogr. A 1029 (2004)

217-222.

[19] Q. Li, M. Oshima, S. Motomizu, Flow-injection

spectrouorometric determination of trace amounts

of formaldehyde in water after derivatization with

acetoacetanilide. Talanta, 72 (2007) 1675-1680.

[20] F. Santos de Oliveira, E.T. Sousa, J.B. De Andrade,

A sensitive ow analysis system for the uorimetric

determination of low levels of formaldehyde in

alcoholic beverages. Talanta, 73 (2007) 561-566.

[21] B.X. Li, M.L. Liu, Z.J. Zhang, C.L. Xu, Flow-injection

chemiluminescence determination of formaldehyde

with a bromate-rhodamine 6G system. Anal. Sci., 19

(2003) 1643-1646.

[22] Z.H. Song, S.A. Hou, On-line monitoring

of formaldehyde in water and air using

chemiluminescence detection. Int. J. Environ. Anal.

Chem., 83 (2003) 807-817.

[23] Z.Q. Zhang, H. Zhang, G.F. He, Preconcentration

with membrane cell and adsorptive polarographic

determination of formaldehyde in air, Talanta, 57

(2002) 317-322.

[24] J.H. Tang, X.M. Wang, G.Y. Sheng, J.M. Fu, The

progress of the analysis of formaldehyde and other

carbonyls in atmosphere, Chin. J. Anal. Chem., 1

(2005) 134-140.

[25] C. Zhao, M. Li, K. Jiao, Determination of formaldehyde

by staircase voltammetry based on its electrocatalytic

oxidation at a nickel electrode, J. Anal. Chem., 61

(2006) 1204-1208.

[26] K. Toda, K. Yoshioka, K. Mori, S. Hirata, Portable

system for near-real time measurement of gaseous

formaldehyde by means of parallel scrubber stopped-

ow absorptiometry, Anal. Chim. Acta, 531 (2005)

41-49.

[27] K. Kawamura, K. Kerman, M. Fujihara, N. Nagatani,

T. Hashiba, E. Tamiya, Development of a novel hand-

held formaldehyde gas sensor for the rapid detection

of sick building syndrome, Sens. Actuators B, 105

(2005) 495.

[28] L. Campanella, M. Battilotti, R. Dragone, I. Mevola,

Suitable solid state chemical sensor for HCHO

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

determination. Int. J. Environ. Pollut., 27 (2006) 313-

323.

[29] EFOA, European Fuel Oxygenates Association, Fuel

ethers and gasoline, available at http://www.efoa.org

(Accessed May 26, 2016).

[30] B. Allen, MTBE friend or foe, Green Chem., (1999)

142-151.

[31] D.A. Cassada, Y. Zhang, R.F. Spalding, Trace analysis

of ethanol, MTBE, and related oxygenate compounds

in water using solid phase microextraction and gas

Chromatography/Mass spectrometry, Anal. Chem., 72

(2000) 4654-4658.

[32] United States Environmental Protection Agency

(USEPA), Ofce of research and development,

oxygenates in Water: critical information and research,

EPA/600/R-98/048, Washington, DC, 2018.

[33] C.D. Church, L.M. Isabelle, J.F. Pankow, D.L. Rose,

P.G. Tratnyek, Method for determination of methyl

tert-Butyl ether and its degradation products in water,

Environ. Sci. Technol., 31 (1997) 3723-3726.

[34] L. Zwank, T.C. Schmidt, S.B. Haderlein, M. Berg,

Simultaneous determination of fuel oxygenates

and BTEX using direct aqueous injection gas

chromatography mass spectrometry (DAI-GC-MS).

Environ. Sci. Technol., 36 (2002) 2054-2059.

[35] B. Nouri, B. Fouillet, G. Touissaint, R. Chambon, P.

Chambon, Complementarity of purge-and-trap and

head-space capillary gas chromatographic methods

for determination of methyl-tert.-butyl ether in water,

J.Chromatogr., A 726 (1996) 153-159.

[36] C. Achten, W. Püttmann, Determination of methyl

tert-Butyl Ether in surface water by use of solid phase

microextraction. Environ. Sci. Technol., 34 (2000)

1359-1364.

[37] C. Achten, K. Axel, W. Püttmann, Sensitive method for

determination of methyl tert-butyl ether (MTBE) in

water by use of HS-SPME/GC-MS. Fresenius J.Anal.

Chem., 371 (2001) 519-525.

[38] L. Black, D. Fine, High levels of monoaromatic

compounds limit the use of solid phase microextraction

of methyl tert-butyl ether and tert-butyl alcohol.

Environ. Sci. Technol., 35 (2001) 3190-3192.

[39] D,A. Cassada, Y. Zhang, R.F. Spalding, Trace analysis

of ethanol, MTBE, and related oxygenate compounds

in water using solid phase microextraction and gas

Chromatography/Mass spectrometry. Anal.Chem., 72

(2004) 4654.

[40] I. Arambarri, M. Lasa, R. Garcia, E. Millán,

Determination of fuel dialkyl ethers and BTEX in

water using headspace solid-phase microextraction

and gas chromatography–ame ionization detection,

J.Chromatogr., A 1033 (2004) 193-203.

[41] F. Fang, C.S. Hong, S. Chu, W. Kou, A. Bucciferro,

Reevaluation of headspace solid-phase microextraction

and gas chromatography–mass spectrometry for the

determination of methyl tert-butyl ether in water

samples, J.Chromatogr., A 1021 (2003) 157-164.

[42] J. Dron, R. Garcia, E. Millan, Optimization of

headspace solid-phase microextraction by means of an

experimental design for the determination of methyl

tert.-butyl ether in water by gas chromatography–

ame ionization detection, J. Chromatogr., A 963

(2002) 259-264.

[43] F.L. Cardinali, D.L. Ashley, J.C. Morrow, D.M. Moll,

B.C. Blount, Measurement of trihalomethanes and

methyl tertiary-butyl ether in tap water using solid-

phase microextraction GC-MS, J. Chromatogr. Sci.,

42 (2004) 200-206.

[44] S. Nkamura, S. Daishima, Simultaneous determination

of 22 volatile organic compounds, methyl-tert-butyl

ether, 1,4-dioxane, 2-methylisoborneol and geosmin

in water by headspace solid phase microextraction-

gas chromatography–mass spectrometry, Anal. Chem.

Acta, 548 (2005) 79-85.

[45] A.S. Yazdi, H. Assadi, Determination of trace of methyl

tert-butyl ether in water using liquid drop headspace

sampling and GC, Chromatographia, 60 (2004) 699-

702.

[46] N. Bahramifar, Y. Yamini. S. Shariat-Feizabadi,

M. Shamsipur, Trace analysis of methyl tert-butyl

ether in water samples using headspace solvent

microextraction and gas chromatography–ame

ionization detection, J. Chromatogr., A 1042 (2004)

211-217.

[47] M.P. Munoz, F.J.M. De Villena Rueda, L.M.P.

Diez, Determination of formaldehyde in air by ow

injection using pararosaniline and spectrophotometric

detection, Analyst, 114 (1989) 1469-1471.

[48] L. Kirkup, M. Mulholland, Comparison of linear

and non-linear equations for univariate calibration, J.

Chromatogr., A 1029 (2004) 1-11.

[49] Standard test method (ASTM D5197) for determination

of formaldehyde and other carbonyl compounds in air,

Philadelphia, USA, 2018.

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

Ehsan Zolfonoun a,*

a Material and Nuclear Fuel Research school, Nuclear Science and Technology Research Institute, Tehran, Iran

to food products and pharmaceutical formulas to

correct possible dietary deficiencies [3]. Therefore,

reliable analytical methods for the determination of

Trp are of great interest.

A variety of analytical methods have been

described for the determination of Trp, including

high performance liquid chromatography

(HPLC) [4], capillary electrophoresis [5],

electroanalytical methods [6], spectrophotometry

and spectrofluorimetry [7, 8]. Compares with the

Chromatographic methods, spectrofluorimetric

determination is a simple, fast and inexpensive

method. However, the direct determination of

Trp at low concentrations by spectrofluorimetry



preconcentration using multi-walled carbon nanotubes

1. Introduction

Analysis of amino acids is important in several

fields of research, particularly in food,

soil, biotechnology and pharmaceutical

industries [1, 2]. Tryptophan (2-Amino-3-

(1H-indol-3-yl) propanoic acid) (Trp) is an

essential amino acid for humans and is required

for the biosynthesis of proteins and also is

important in nitrogen balance in adults. This

amino acid cannot be synthesized in the human

body and must be obtained from food or

supplements. Tryptophan is sometimes added

*Corresponding author: Ehsan Zolfonoun

Email: ezolfonoun@aeoi.org.ir

https://doi.org/10.24200/amecj.v2.i01.43

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

Received 10 Jan 2019

Revised form 3 Feb 2019

Accepted 23 Feb 2019

Available online 19 Mar 2019

Keywords:

L-tryptophan

Solid-phase extraction

Multi-walled carbon nanotubes

Bioanalysis

Spectrofluorometry

A B S T R A C T

A solid-phase extraction method based on multi-walled carbon

nanotubes (MWCNTs) was applied for the preconcentration of

L-tryptophan (  prior to its spectrofluorometric

determination. Due to the high surface area of MWCNTs, satisfactory

concentration factor and extraction recovery can be achieved with only

10 mg MWCNTs in 5 min. The effects of pH, sorbent amount, eluent

type and time on the recovery of the analyte were investigated. Under

the optimum conditions, the detection limit for L-tryptophan was 8.9

ng mL. The precision of the method, evaluated as the relative

standard deviation obtained by analyzing of 10 replicates, was 2.6%.

The practical applicability of the developed method was examined

using wheat and barley samples.

Bio-Extraction of L-tryptophan by carbon nanotubes; Ehsan Zolfonoun

Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 43-48

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

is difficult because of insufficient sensitivity of

this technique as well as the matrix interferences

occurring in real samples, and an initial sample

pretreatment, such as preconcentration of the

analyte, is often necessary [9, 10].

Solid phase extraction (SPE) is a routine extraction

method for preconcentration of organic and

inorganic analytes. This technique reduces solvent

usage and exposure, disposal costs, and extraction

time. Various adsorbents, such as octadecyl

functional groups bonded on silica gel, C18 [11],

silica gel [12], chelating adsorbents [13], Amberlite

XAD resins [14, 15], activated carbon [16] and

other sorbents [17] have been used for adsorption

of analytes in SPE methods.

Multi-walled carbon nanotubes (MWCNTs) have

received great attention due to their exceptional

electronic, mechanical, thermal, chemical

properties and significant potential applications in

many fields [18]. Owing to their large surface area

and high reactivity, MWCNTs based adsorbents

have been used for solid phase extraction and

preconcentration of organic compounds and metal

ions [19, 20]. Compared with traditional SPE

sorbents, MWCNTs offer a significantly higher

surface area-to-volume ratio and a short diffusion

route, resulting in high extraction capacity, low

extraction time and high extraction efficiencies

[21].

In this paper, a magnetic solid phase extraction

method based on multi-walled carbon nanotubes is

developed for the extraction and preconcentration

of L-tryptophan(α-amino acid), prior to its

spectrofluorometric determination.

2. Experimental

2.1. Reagents

All reagents used were of analytical grade and

were used as supplied. NaOH, ammonia solution,

were purchased from Merck (Germany). MWCNTs

(purity> 95%) were obtained from Sigma-Aldrich.

Standard stock solution (1000 μg mL–1) of

L-tryptophan was prepared by dissolving the pure

solid (Sigma-Aldrich) in deionized water. Working

solutions were prepared daily by adequate dilution

with deionized water.

2.2. Instrumentation

The fluorescence measurements were performed

using a Perkin-Elmer LS50 spectrofluorometer,

equipped with a xenon discharge lamp. A Metrohm

model 744 digital pH meter, equipped with a

combined glass-calomel electrode, was employed

for the pH adjustments.

2.3. solid-phase extraction procedure

A 40 mL sample or standard solution containing

L-Trp (pH 6) was transferred in a polypropylene

centrifuge tube. Then 10 mg of MWCNTs was

added into the sample solution. The mixture was

shaken for 5 min. The solution was centrifuged

for 5 min at 5,000 rpm, and the aqueous phase

was removed. The preconcentrated target analyte

was eluted using 1.0 mL of a 2 mol L−1 solution of

NaOH. The pH of this solution was adjusted at 10

by addition of 2 mol L−1 hydrochloric acid and then

solution made up to 2.0 ml with deionized water.

Finally, the concentration of L-tryptophan was

determined spectrofluorometrically at λem = 360

nm after excitation at 274 nm.

2.4. Sample preparation

For digestion of wheat and barley samples, 20.0 mL

KOH (10 % m/v) were added to 0.20 g of sample

powder in a 100.0 mL conical flask to hydrolyze

in an oven at 40 °C for 16–18 h. Then, the mixture

was filtered through a filter paper and adjusted

to pH 6 by the addition of 6 M HCI. Finally the

solution made up to 50.0 ml with deionized water.

3. Results and discussion

3.1. Optimization of extraction conditions

3.1.1. Effect of pH

The effect of pH on the extraction of L-Trp was

studied in the range of 3.0–11.0 using nitric acid or

ammonium acetate. The resulting percent recovery-

pH plot is shown in Fig. 1, which indicates that

sorption is maximum and quantitative in the pH

range 3.0–9.0. Therefore, pH 6.0 was selected for

further study.

Bio-Extraction of L-tryptophan by carbon nanotubes; Ehsan Zolfonoun

3.1.2. Effect of the sorbent amount

In comparison with the traditional sorbents,

MWCNTs offer a significantly higher surface area-

to-volume ratio. Therefore, satisfactory results can

be achieved with fewer amounts of MWCNTs. In

order to study the effect of the sorbent, 2 to 20 mg

of MWCNTs was added to 40 mL of the sample

solution (Fig. 2). The obtained results showed that

by increasing the sorbent amounts from 2 up to 10

mg due to increasing accessible sites, extraction

recovery increased and after that remained

constant. A 10 mg of the MWCNTs was selected

for subsequent experiments.

3.1.3. Effect of eluent type

In order to find the best eluent, different eluting

solutions such as HCl, HNO3, acetic acid, NaOH,

were tested. Obtained results showed that among

the tested eluent, NaOH was found to be the superior

solvent in comparison with other solvents for

desorption of analytes from surface of the sorbent.

Therefore, NaOH solution was selected and used as

an eluent. The effect of NaOH concentration on the

recovery of the adsorbed L-Trp was examined in

the range of 0.1 to 5 mol L (Fig. 3). Based on the

obtained results, 2.0 mol L NaOH was sufficient

for complete elution of the adsorbed Trp on the

sorbent surface. To achieve the highest recovery

Fig. 1. Effect of pH on the extraction efficiency of L-Trp. Conditions: sample volume, 40 mL; MWCNTs amount,

10 mg; Concentration of L-Trp, 0.10 µg mL–1.

Fig. 2. Effect of the MWCNTs amount on the recovery of L-Trp. Conditions: pH, 6, sample volume, 40

mL; Concentration of L-Trp: 10 µg mL–1.

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

of the adsorbed L-Trp, the effect of the volume of

the eluent was also tested. The minimum volume

of NaOH required for quantitative elution of the

retained analyte was 1.0 mL.

3.1.4. Effect of extraction time

The effect of extraction time on the extraction of

L-Trp was studied in the range of 1–15 min. The

experimental results indicated that there was no

significant effect on the extraction efficiency when

the extraction time increased from 5 to 15 min.

Based on the above considerations, 5 min was

selected for further studies.

3.1.5. Sorption capacity

In order to determine the maximum capacity for

L-Trp, 20 mg of the adsorbent was added to 40

mL of an aqueous solution containing 20 mg L–1

L-Trp and shaken it for 30 min under optimized

conditions. After decantation of the sorbent, the

concentration of retained L-Trp in the supernatant

solution was determined. The maximum capacity

was found to be 36.3 mg g–1 for L-Trp.

3.2. Analytical gures of merit

Table 1 summarizes the analytical characteristics of

the proposed method, including linear range, limit

of detection, reproducibility, and enhancement

factor. In the optimum conditions, a calibration

graph was constructed by preconcentrating a series

of the solutions according to the procedure under

experimental. The linear regression equation for

the calibration graph for the concentration range

   was I=92.69C+74.43

(r2=0.9984, n=8), where I is the fluorescence

intensity and C is Trp concentration in the sample

solution in  mL.

The limit of detection (LOD) of the proposed

method for the determination of Trp was studied

under the optimal experimental conditions. The

LOD, defined as three times the standard deviation

of 10 measurements of the blank solution divided

by the slope of the calibration curve, was 8.9 ng

mL. The reproducibility of the proposed method

for extraction and determination of 0.10 µg mL

Trp (n= 10) was also studied. The relative standard

deviation (R.S.D.) of these determinations was 2.6

3.3. Application

The proposed method was applied to the

determination of L-Trp in wheat and barley samples

Table 1. Analytical parameters of the proposed method.

Parameter Analytical feature

Linear range (µg mL)

Calibration equation I=92.69C+74.43

r20.9984

LOD (ng mL) 8.9

R.S.D. % (n = 10) 2.6

Fig. 3. Effect of NaOH concentration on the extraction efficiency of L-Trp. Conditions: pH, 6, sample volume, 40

mL; MWCNTs-Fe3O4 amount, 10 mg; Concentration of L-Trp, 0.10 µg mL–1.

Bio-Extraction of L-tryptophan by carbon nanotubes; Ehsan Zolfonoun

and the obtained results by proposed method were

compared with HPLC method. The results obtained

are shown in Tables 2. The results demonstrated

that the proposed method was suitable for the

determination of L-Trp in real samples.

4. Conclusions

A simple and fast SPE method based on MWCNTs

was developed for the preconcentration and

spectrofluorimetric determination of L-Trp. The use

of NPs endued the SPE method with high extraction

capacity and preconcentration factors. Also using

spectrofluorimetry as a detection system exhibits

a low primary and operational cost in comparison

with other methods such as HPLC. The method

can be successfully applied to the separation and

determination of tryptophan in real samples.

5. References

[1] W. Amelung, X. Zhang, K.W. Flach, Amino acids in

grassland soils: climatic effects on concentrations

and chirality, Geoderma, 130 (2006) 207-217.

[2] M. Ikeda, Amino Acid Production Processes. Adv.

Biochem. Eng. Biotechnol. 79 (2002) 1-35.

[3]    

S. Jiménez-Pérez, F.J. Morales, Tryptophan

determination in milk-based ingredients and dried

sport supplements by liquid chromatography with

     

580-585.

[4] D.I. Sanchez-Machado, B. Chavira-Willys, J.

Lopez-Cervantes, High-performance liquid

    

quantitation of tryptophan and tyrosine in a shrimp

waste protein concentrate, J Chromatogr., 863

(2008) 88–93.

[5] Takagai Y, Igarashi S. Determination of ppb levels of

tryptophan derivatives by capillary electrophoresis

with homogeneous liquid–liquid extraction and

sweeping method, Chem. Pharm. Bull., 51 (2003)

373-377.

[6] A.R. Fiorucci, E.T.G. Cavalheiro, The use of

carbon paste electrode in the direct voltammetric

determination of tryptophan in pharmaceutical

formulations, J. Pharm. Biomed. Anal., 28 (2002)

909-915.

[7] J. Ren, M. Zhao, J. Wang, C. Cui, B. Yang,

Spectrophotometric method for determination of

tryptophan in protein hydrolysates, Food Technol.

Biotechnol., 45 (2007) 360-366.

[8] A.M. Othmana, S. Lib, R.M. Leblancb, Enhancing

    

tryptophan by using graphene oxide nanosheets,

Anal. Chim. Acta, 787 (2013) 226-232.

[9] H. Abdolmohammad-Zadeh, S.M. Hammami-

Oskooyi, Solid-phase extraction of l-tryptophan

from food samples utilizing a layered double

hydroxide nano-sorbent prior to its determination

      

(2015) 1115-1122.

[10]   2 coupled with

    

analysis of L-tryptophan, Anal. Biochem., 401

(2010) 260-265.

[11] E. Zolfonoun, A. Rouhollahi, A. Semnani, Solid-

phase extraction and determination of ultra trace

amounts of lead, mercury and cadmium in water

samples using octadecyl silica membrane disks

   

and atomic absorption spectrometry, Int. J. Environ.

Anal. Chem., 88 (2008) 327-336.

[12] N. Wanga, X. Liang, Q. Li, Y. Liao, S. Shao, Nitro-

 

silica gel as a sorbent for solid-phase extraction of



[13]        

Novel chelating resin for solid-phase extraction of



Anal. Lett., 50 (2017) 364-378.

[14] J.B. Ghasemi, E. Zolfonoun, Simultaneous

spectrophotometric determination of trace amounts

of uranium, thorium, and zirconium using the partial

least squares method after their preconcentration by

    

resin, Talanta, 80 (2010) 1191-1197.

[15] K. Saberyan, E. Zolfonoun, M. Shamsipur, M.

Salavati-Niasari, Separation and preconcentration

Table 2. Determination of tryptophan in food samples.

Tryptophan (mg/g)Sample

HPLCProposed method

1.631.54 ± 0.04 Wheat

1.141.26 ± 0.03Barley

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

of trace gallium and indium by amberlite XAD-

7 resin impregnated with a new hexadentates

naphthol-derivative schiff base, Sep. Sci. Technol.,

44 (2009) 1851-1868.

[16] Z.A. Alothman, E. Yilmaz, M. Habila, M.

Soylak, Solid phase extraction of metal ions in

environmental samples on 1-(2-pyridylazo)-2-

naphthol impregnated activated carbon cloth,

Ecotoxicol. Environ. Saf., 112 (2015) 74-79.

[17] H. Ebrahimzadeh, M. Behbahani, A novel lead

imprinted polymer as the selective solid phase for



atomic absorption spectrophotometry: Synthesis,

characterization and analytical application, Arab. J.

Chem., 12 (2017) 2499-2508.

[18] R.H. Baughman, A.A. Zakhidov, W.A. deHeer,

Carbon nanotubes-the route toward applications,

Science, 297 (2002) 787-792.

[19] D. Pardasani, P.K. Kanaujia, A.K. Purohit, A.R.

Shrivastava, D.K. Dubey, Magnetic multi-walled

carbon nanotubes assisted dispersive solid phase

extraction of nerve agents and their markers from

muddy water, Talanta, 86 (2011) 248-55.

[20] E. Stanisz, M. Krawczyk, H. Matusiewicz,

Solid-phase extraction with multiwalled carbon

nanotubes prior to photochemical generation of

cadmium coupled to high-resolution continuum

source atomic absorption spectrometry, J. Anal. At.

Spectrom., 29 (2014) 2388-2397.

[21] D. Shao, C. Chen, X. Wang, Application of

polyaniline and multiwalled carbon nanotube

magnetic composites for removal of Pb(II), Chem.

Eng. J., 185 (2012) 144-150.

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

1. Introduction

In recent decades, the various pollutants are

being detected in urban areas which are mainly

caused by fossil fuel components. They include

a wide spectrum of hydrocarbons. The aromatic

hydrocarbons are either bio-chemically or

biologically active and are potentially carcinogenic

or are by-products of benzene. Many of the recent

researches indicate the adverse effects of benzene

on human health. Although VOCs are quite

important, there have been few studies conducted in

this regard in Tehran metropolitan [1-2]. The main

emphasis has been on measurement, monitoring

and control of VOCs in the last 10 years. The

concentration of hydrocarbons in Tehran is much

higher than other cities in the world (the benzene

and butadiene 1 & 3 levels in Tehran are 10 and 18

times the permissible standards). [2].

Amongst the hydrocarbons, benzene due

* Corresponding Author.A.Mirzahosseini

E-mail: mirzahosseini@gmail.com

https://doi.org/10.24200/amecj.v2.i01.47

Seyed Alireza Hajiseyed Mirzahosseinia,*

a Department of Environmental Engineering, Faculty of Natural Resources and Environment, Science and Research Branch, Islamic Azad University,

Tehran, Iran

Environmental Health Analysis: Assessing the emission levels of

benzene from the fuel tanks doors of the vehicles in Tehran city

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

Received 16 Jan 2019

Revised form12 Feb 2019

Accepted 30 Feb 2019

Available online 19 Mar 2019

Keywords:

Volatile Organic Compounds

Benzene emission

PhoCheck

Domestic cars

Analysis of benzene in Air

A B S T R A C T

In this study, 350 vehicles in 20 different models were examined in

one of Tehran’s Automobile Technical Inspection Centers. The laboratory

tests indicate that longtime exposure to benzene has destructive effects

on the blood cells, especially the bone-marrow cells. The concentration

levels of benzene caused by the emission of gasoline vapors from fuel

tanks doors were measured by PhoCheck EX5000 during a 5 to 15-

minute interval for each car. The results indicate that the concentration of

benzene caused by the emission of gasoline vapors from the fuel tanks

door of the domestic cars was 10 times higher than the imported cars. In

most of the imported cars, the amount of benzene in the three measured

areas was negligible. This is due to the use of new technology and

adaptation of strict environmental standards by the manufacturing country.

Emission levels of benzene from the fuel tanks; Seyed Alireza Hajiseyed Mirzahosseini

Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 49-54

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

to its carcinogenic effects has an especial

importance. The main sources of benzene

emission in Tehran are the motor vehicles

and the gas stations (due to the evaporation

of fuel and lack of the fume control system).

Majority of the vehicles in Tehran are run

on gasoline and regrettably, their consumed

gasoline has high benzene content (about

5% of the weight). Moreover, most of the

automobiles manufactured domestically lack

environmental standards. They can only attain

Euro 2 Standard that was ratified in 1996.

This is done through modifications in their

appearance and the pollution control systems.

Meanwhile, the production lines of reference

companies like Peugeot 405 and Kia Pride

have stopped abroad more than a decade ago.

It is important to point out that the two major

auto manufactures of Iran, namely SAIPA and

Iran Khodro assemble the decade-old products

of the aforesaid companies. [2]

Various studies are conducted on the effect

of domestically produced fuel and vehicles’

quality on air pollution. Similar researches

are conducted in Brazil and Pakistan.[ 3-4].

Batterman in 2005 studied the amount of

benzene emitted from the fuel tank. Based on

his measurements, the average level of benzene

emission was 2 milligrams per hour. For old

vehicles, this amount reached 62 milligrams

per hour. In this study, the replacement of the

gas cap and the washer of the fuel tank were

regarded as measures to reduce the amount of

evaporated fumes [5]. It is important to point

out that the Iranian and international standard

level of benzene in ambient air is 1.56 ppb

and in advanced countries like Japan is 0.69

ppb. For most countries in the world, the Euro

4 standard was used in 2005[6].

The laboratory tests indicate that longtime exposure

to benzene has destructive effects on the blood cells,

especially the bone-marrow cells. These effects

cause the reduction in production of bone-marrow

cells and anemia. The long term effect of benzene is

leukemia. Environment Protection Agency (EPA)

categorizes benzene in group A of carcinogenic

substances. Also, the International Agency for

Research on Cancer (IARC) refers to benzene as a

carcinogenic substance for humans[7-9].

2. Material and Methods

In this research, the benzene concentration is

measured by PhoCheck EX5000 equipment.

This device is portable and with the aid of Photo

Ionization Detector (PID) mechanism can measure

the benzene concentration level with high precision

(± 1 ppb). The PhoCheck takes samples from the

gasoline fumes with the flow rate of 220 millimeters

per minute. This device with its high precision

(ppb level) samples the benzene through a portable

laboratory chromatograph. It is important to point

out that Krypton lamp of 10.6 eV is used in this

device. One of the most important advantages of this

equipment is its approved technology to determine

the benzene concentration with the accuracy of 1

ppb to 10000 ppm as well as its good performance

in weathers ranging from -20 to 60 degrees[10].

In this study, 350 automobiles encompassing

20 models are examined in the Automobile

Technical Inspection Center of Tehran. The

benzene concentration due to the gasoline fume

is measured at three important spots namely,

the gas cap, muffler and inside the cabin during

a period of 5 to 10 minutes (for each car). It

Emission levels of benzene from the fuel tanks; Seyed Alireza Hajiseyed Mirzahosseini

is important to point out that all the cars were

tested for the fume emission, after they received

their certificate from the Technical Inspection

Center. All the Iranian made cars are required

to be inspected annually after the 2nd years of

production and obtain the certificate. For the

ease of study, 350 automobiles were divided

into two categories’ of imported and domestic

vehicles.

In most of the studied cars, there were three

protective valves for the gas cap (except the

Peugeot 206). The protective valve has a physical

function without being in direct contact with the

gasoline and its fumes. However, if the first valve

(which is in direct contact with the gasoline and the

fumes) fails, the leaked fumes would enter the small

chamber of the protective valve for subsequent

release to the atmosphere.

The second valve plays its role in controlling the

fumes and the overflow of gasoline. In most of the

domestically manufactured cars (except Renault

L90), this valve does not exist. Figure1 illustrates

the position of the three valves and the means to

measure benzene. During measurement, the engine

is off and only the protective valve is open. Since the

valve in Peugeot 206 is in one piece, only the space

between the chassis and the gas cap is sampled.

Unfortunately, in Peugeot 405 with carburetor, the

Table 1. The minimum, maximum and average concentration levels of benzene in 12 models of imported cars (the

amounts are in ppb)

Car Type Hyundai Nissan Mazda Gol Kia Zantia Roniz Cielo Toyota Prado Benz BMW

Average 0.03 0.98 0.21 0.86 0.16 0.34 2.34 0.57 0.68 0.12 0.15 0.1

Max 0.397 3.6 0.83 9.4 0.98 0.97 6.9 2.3 4.3 0.3 0.73 0.7

Min 0 0 0 0.82 0 0 0 0 0 0 0 0

Fig. 1. Sampling method of the fuel tank, the protective valve, primary and secondary valves (if present)

3-Primary valve

2-Secondary valve

1-Protective valve

Protective valve

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

gasoline fume was emitted from other parts of the

car (underneath the fuel tank and the engine).

3. Results and Discussion

3.1. concentration levels of benzene in 12 models

of imported cars

The imported automobiles consisted of 116

vehicles from 12 company models. The results

indicated that Gol (manufactured by Volkswagen)

has the highest amount of benzene leakage from

the gas cap. The average concentration of benzene

in this group is 86.5 ppb. The lowest concentrations

of benzene were detected in Hyundai, Kia,

Mercedes Benz, BMW and Prado in amounts of

0.03 ppb, 0.16 ppb, 0.15 ppb, 0.01 ppb and 0.12

ppb, respectively. It is important to point out that

Mercedes Benz and BMW models in 70 percent of

the cases registered zero concentrations (the best

condition). With respect to the fuel type (super and

regular gasoline), 28 percent of the samples used

were super unleaded gasoline (Octane number of

95) and 72 percent were regular unleaded gasoline

(Octane number of 87). The average age of the

vehicles in this classification was 3.8 years. About

65 percent of the sampled automobiles had less

than 3 years of operation.

In Table (1), the minimum, maximum and average

concentrations of benzene are provided. The

minimum amounts of measured benzene in all

models, except Gol, were zero. Gol model showed

the highest benzene leakage from the gas tank.

It is important to point out that the most important

reasons for the emission of benzene fumes in this

category are lack of tightening the gas cap and

over fueling (pumping too much gasoline into the

fuel tank). The average concentration of emitted

benzene from the fuel tank of the imported vehicles

(116 automobiles) is 0.96 ppb.

3.2. concentration levels of benzene in 8 models of

domestic vehicles

In the domestically manufactured auto category,

a total of 234 cars in eight various models are

investigated. Based on the results, Paykan and

Pride show the highest leakage of benzene from the

gas cap with the average benzene concentrations

of 21.76 and 86.43 ppb, respectively. It should be

pointed out that the average age of the examined

automobiles was 4.8 years, where 65% of the

sampled cars had less than 5 years of age. In regard

to the fuel type consumption, the super and regular

gasoline was used 22.2% and 77.8%, respectively.

The lowest concentrations of benzene are detected

in Rio and Peugeot 206 as 0.43 and 3.09 ppb,

respectively. It is important to mention that Peugeot

206 has registered zero concentration in over 35%

of its samples. Table 2 presents the minimum,

maximum and average benzene concentration.

It reveals that the minimum benzene concentration

in all models except Paykan was zero. The primary

Table 2. The minimum, maximum and average concentration of benzene in domestic vehicles in 8 models (measured

in ppb)

Car Type Tondar 90 Paykan Pars 405 206 Pride Samand Rio

Average 6.59 76.21 26.21 6.83 3.09 43.86 3.94 0.43

Max 38.2 296 151 59.6 51.5 295 7.35 1.95

Min 0 2.06 0 0 0 0 0 0

Emission levels of benzene from the fuel tanks; Seyed Alireza Hajiseyed Mirzahosseini

reasons for the emission of benzene fumes in this

group are technical defects of the primary gas

cap, lack of the secondary gas cap, over fueling

and lack of canister system. Also, about 9% of

the domesticated vehicles run on carburetors

whose average benzene concentration (in 234

automobiles) is 20.89 ppb. As it is shown in Table

2-2, the emission from the gas caps goes up as the

age of the vehicle increases.

4. Conclusions

Majority of the domestic cars emit high levels

of benzene from the gas cap, muffler and the

gas tank. The best and worst domestically

manufactured automobiles are Peugeot 206 and

Pride, respectively. The most prominent reasons for

high concentration of benzene in this category are

the lack of appropriate catalyst system, technical

defects in fuel system, and fuel leakage from the

gas cap. Amongst the imported car category, Kia

and Hyundai groups have the lowest emission of

benzene. In most of the imported cars, the amount

of benzene in the three measured areas was

negligible. This is due to the use of new technology

and adaptation of strict environmental standards by

the manufacturing country.

Based on the research results, the amount of benzene

concentration due to the leakage of gasoline fumes

from the gas cap in domestic cars is approximately

ten times higher than the imported cars. In Pride

models, the level of gasoline fume emission is

considerable and the benzene concentration is

15 times higher than Peugeot 206. Moreover, the

average benzene concentration from the emission

of gasoline fumes from the gas cap of the imported

cars is less than 6 ppb. However, this number for

much of domestic cars was higher than 6 ppb. Pride

is identified as the most polluting vehicle in the

domestic car category. The research results indicate

that the annual inspect of the gas tank, periodical

replacement of washer, and modification of the gas

cap system in the domestic cars have significant

impact on the reduction of gasoline fumes.

5. References

[1] A. Karbasi, S. Khoramnezhadian, S. Asemi Zavareh,

Gh, Pejman Sani, Determination of the emission

rate and modeling of benzene dispersion due to

surface evaporation from an oil pit, J. Air Pollut.

Health, 3, 3 (2018) 155-166.

[2] F. Atabi, SAH. Mirzahosseini, GIS-based assessment

of cancer risk due to benzene in Tehran ambient air,

Int. J. Occup. Med. Environ. Health, 26, 5 (2013)

770–779.

[3] N.V. Heeb, A. M. Forss, C. Bach, Fast and quantitative

measurement of benzene, toluene and C2 benzene’s

in an automotive exhaust during tran-sient engine

operation with and without catalytic exhaust

treatment, Atmos. Environ, 33 (1999) 205–215.

[4] GT. Johnson, SC. Harbison, JD. McCluskey, RD.

Harbison, Characterization of cancer risk from

airborne benzene exposure. Regul. Toxicol. Pharm;

55 (2009) 361–366

[5] S. Batterman, G. Hatzivasilis, C. Jia, Concentrations

and emissions of gasoline and other vapors from

residential vehicle garages. Atm. Environ., 40

(2006) 1828–1844.

[6] H. Kajihara, S. Ishizuka, A. Fushimi, A. Masuda, J.

Nakanishi, Population risk assessment of ambient

benzene and evaluation of benzene regulation in

gasoline in Japan. Environ. Eng. Policy, 2 (2000)

1–9.

[7] Agency for Toxic Substances and Disease Registry



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

U.S. Public Health Service, U.S. Department of

Health and Human Services, Atlanta, GA. (1997).

[8] S. Wilbur, ATSDR evaluation of potential for human

exposure to benzene, Toxicol. Ind. Health, 24

(2008) 399–442.

[9] Department of the Environment and Heritage,

Technical Report No.6: BTEX Personal Exposure

Monitoring in Four Cities in Australia, Published

by Environment Australia, (2003).

[10] PhoCheck Instrument, user manual V2.6, Ion

Science Company(ISC), 2012. http://www.

ionscience.com/products/phocheck-plus-handheld-

voc-gas-detector#downloads, 2012

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

1. Introduction

Heavy metals are a group of elements with a mass

density greater than 4.5 g cm-3, which tend to release

electrons in chemical reactions and form simple

cations. Heavy metals such as, Cd, Ni, Co, Cr, and

Pb is potentially toxic; in addition, their effects in

water, plants, and soil are very important. Prolonged

accumulation of heavy metals through food stuff

may lead to chronic effect in the nerve system,

kidney and liver of humans [1-4]. The sources of

anthropogenic contamination or pollution of the

environment by heavy metals include different

branches of industry, the power industry, transport,

municipal waste management, waste dumping

sites, fertilizers and waste used to fertilize soil. The

heavy metals from these sources are dispersed in the

environment and they contaminate soil and water.

They also (directly or indirectly through plants) get

into human and animal bodies. After entering heavy

metals from water or soil to vegetables these metals

can enter people’s diet and consequently exert their

effects. Soil chemical composition plays important

role in composition of plant materials. Overall

toxic metal availability in soil contributes to metal

contents in vegetables. Soil eco-system throughout

Shahnaz Teimooria,*

a Department of Environment and Natural Resources, Islamic Azad University, Science and Research Branch, Tehran, Iran

Environmental Health: Evaluation of heavy metals pollution in

Isfahan industrial zone from soils, well / eluent waters and waste

water by microwave- electro-thermal atomic absorption spectrometry

*Corresponding Author: Shahnaz Teimoori

E-mail: sht9737@gmail.com

https://doi.org/10.24200/amecj.v2.i01.44

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

Received 1 Feb 2019

Revised form 24 Feb 2019

Accepted 8 Mar 2019

Available online 20 Mar 2019

Keywords:

Heavy Metals

Environmental Pollution

Waters and Soils

Electro-thermal Atomic

Absorption Spectrometry

A B S T R A C T

In this study, soils, well waters, drinking waters, and waste water in the

Isfahan industrial area were sampled in spring and summer 2018. In

8 points of industrial zone, important toxic heavy metals such as, lead

(Pb), Cobalt (Co), Nickel (Ni), Chromium (Cr), and Cadmium (Cd) were

sampled from surface soil (up to 2 m), well/drinking waters and waste

water. After sample preparation with micro-wave digestion technique, the

concentration of heavy metals was determined by electro-thermal atomic

absorption spectrometry (ET-AAS). According to the well water analysis,



L-1-1-1-1-1, respectively. In well

water, the concentrations of Cd, Ni, Cr and Co were found much higher

than Pb in comparison with the references of World Health Organization

(WHO). Also, the concentrations of such elements in soils and drinking

waters are less and near found in accordance to EPA and WHO references

respectively. In addition, the concentration of metals in waste water of

industrial area was more than well waters. Therefore, the pollution of

heavy metals such as Cr, Co, Cd, and Ni in wastewaters of industries can

be diffused to well waters and eluent waters in this region and cause many

problems in plants and humans.

Evaluation of heavy metals pollution in Isfahan; Shahnaz Teimoori

Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 55-62

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

world has been contaminated with heavy metals by

various human activities and movement of metals

in food chain has become human health hazard

[5, 6]. Nickel does not bio-accumulate to a great

extent in animals. There is evidence of uptake and

accumulation in certain plants. Nickel food intake

in the United States ranges is between 69 and



-1. The

US EPA primary drinking water standard is 0.1 mg

L-1 [7]. The trace amount of nickel and cobalt, are

indicated to be either necessary or toxic depending

on their environment concentration range. For

example, due to studies on chicks and rats, nickel

is apparently essential for proper liver function, or

cobalt is at the core of a vitamin B12. On the other

hand, some of nickel and cobalt compounds are

carcinogenic [8–10]. Lead is a common industrial

toxin and environmental pollutant and can enter

the human body. It can affect the nervous system

significantly, especially on the central nervous

system. Industrial development has paid attention

to the adverse effects of lead pollution on people’s

health [11]. A series of literatures also showed

that even if children’s blood lead levels below 10

 -1, they can appear significant neurological

dysfunction. Some researchers showed that many

rivers had lost its self-purification capacity because

of receiving so many industrial wastewaters

[12-14]. Cadmium is highly toxic and has been

implicated in some cases of poisoning through food.

Minute quantities of cadmium are suspected of

being responsible for adverse changes in arteries of

human kidneys. The FAO-recommended maximum

-1.

USEPA drinking water standard for cadmium is

0.005 mg L-1 [15]. Chromium can enter the human

body through breathing, food and drinking water.

Chromium salts are used extensively in industrial

processes and may enter a water supply through the

discharge of wastes. Chromium may exist in water

supplies in both the hexavalent and the trivalent

state although the trivalent form rarely occurs in

potable water. USEPA drinking water standard for

chromium and FAO recommended the maximum

       -1 [16]. The

World Health Organization (WHO) states that the

 Cr (VI) are considered

to be too high as compared to its Geno toxicity [17-

19]. Thus it is obvious that determination of heavy

metals, at trace level, in water and environmental

samples is of great significance from the public

health and environmental point of view. Wastewater

irrigation has been practiced widespread in the

world [20, 21]. Wastewater irrigation creates

both opportunities and problems in agricultural

source [22]. It provides important water resources

and has the beneficial aspects of adding valuable

plant nutrients and organic matter to soil [23].

However, excessive accumulation of heavy metals

in agricultural soil through wastewater irrigation

may not only result in soil contamination, but also

affect food quality and safety [24]. It is necessary

and important to develop sensitive methods for

determining heavy metals in soil, and water

samples and then, the results must be compared

with World Health Organization (WHO) and

Environmental Protection Agency (EPA) [25, 26].

Various techniques such as, inductively coupled

plasma mass spectrometry [27,28], flame atomic

absorption spectrometry (F-AAS) [29], electro-

thermal atomic absorption spectrometry (ET-

AAS) [30,31] and cold vapor atomic absorption

spectrometry(CV-AAS) [32] have been applied for

the determination of soil and water samples.

The aim of this study was to monitor the toxic heavy

metals such as, Cd, Cr, Ni, Co, and Pb in well waters,

drinking waters, waste waters and soils in Isfahan’s

industrial regions and evaluation of environmental

pollution in this area. After microwave digestion

of samples the concentration of heavy metals

were determined by ET-AAS. The results of data

were analyzed using SPSS statistical programmer,

PHSTAT, and excel computer packages.

2. Experimental procedure

2.1. Apparatus and materials

Determination of heavy metals (Cd, Cr, Ni, Co,

Pb) was performed with a spectra GBC electro-

thermal atomic absorption spectrometer (Plus

Evaluation of heavy metals pollution in Isfahan; Shahnaz Teimoori

932, Australia) using a graphite furnace module

(GF3000, GBC). The operating parameters for

the metal of interest were set as recommended by

the manufacturer. All samples in ET-AAS were



of the solutions were measured by a digital pH

meter (Metrohm 744). Microwave digestions were

carried out with a Multi-wave 3000 (Anton Paar,

100 mL, 20 bar; Austria). The instrumental and

temperature programming for the graphite atomizer

are listed in Table 1 and 2. All reagents were of

ultra-trace analytical grade from Merck Germany.

Cd, Cr, Ni, Co and Pb stock solution was prepared

from an appropriate amount of the nitrate salt of

this analyte as 1000 mg L-1 solution in 0.01 mol L-1

HNO3 (Merck). Standard solutions were prepared

daily by dilution of the stock solution. Ultrapure

      

Continental Water System (Bedford, USA).

2.2. Sampling

In this study, Cr, Co, Ni, Cd and Pb of soil, well

water and drinking in eight different location

of Isfahan industrial area were evaluated. For

sampling, all glass tubes were washed with a 1 mol

L-1 HNO3 solution for at least 24h and thoroughly

rinsed 8times with ultrapure water before use. As

determination of heavy metals concentration in

soil samples are very difficult, even contamination

at any stage of sampling, sample storage and

handling or analysis has the potential to affect the

accuracy of the results. All samples prepared in the

vicinity of Isfahan industries. Soil and water were

sampled from eight points of Isfahan’s industrial

zone. All of samples prepared from south of

Isfahan province (4*4 km2) (Fig.1). Due to large

study area Global Positioning System (GPS) was

used to determine the actual coordinates of the

sampling sites and to reconfirm the location of the

sampling site during subsequent sampling periods.

Fig 1. Sampling water and soil in the Isfahan oil refinery area, and G point is oil refinery.

Table 1. The instrumental conditions of ET-AAS for determination heavy metals.

Element Cd Co Cr Ni Pb

Lamp current (mA) 4 7 7 4 5

Wave length (nm) 228.8 240.7 357.9 232.0 217.0

Slit width (nm) 0.5 0.2 0.2 0.2 1.0

LOD (µg L-1) 0.05 0.6 0.1 0.8 0.25

LOQ(µg L-1)) 0.2 3 1 5 3

Working range 0.2-1.8 3-45 1-16 5-65 3-40

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

In preliminary studies soil and water investigation

consists of eight locations, in order to determine

and to provide ground information for subsequent

detailed planning of the future work. For soil

sampling multiple sub samples were taken from

each location and then samples were homogenized

into composite sample with stainless spoon and then

sub sampled by spoon into each sample container

to get accurate results.

2.3. General procedure

Five samples of well/drinking water(16×5),

wastewaters (10) and soil(8×5) were collected from

eight Isfahan’s industrial region (N=130). Samples

were placed in polyethylene bags and brought to

laboratory of IPIHR for analysis. All samples were

washed with tap water followed with DDW (double

de-ionized distil water). In the laboratory, the

soil samples after air drying at room temperature

were sieved with nylon mesh (2 mm). The <2 mm

fraction was grinded in an agate and pestle and

passed through a 63 micron sieve. Selected physio-

chemical properties of these soils were analyzed

using standard methods. Soil pH was measured

in suspension of soil to water ratio (1:2 ) using

calibrated pH meter. Briefly, 1 g of the soil sample

was placed in a decomposition polyethylene tube

to which was added 1 mL of 10 % (w/w) H2O2

and 7 mL HNO3 concentrate. The mixture was

digested by heating and irradiating for 60 min by

microwave digestion system (MDS). After heating

the sample at 120 oC the volume of the digested

sample was set to 0.5 mL and dilution up to 3 mL

with DDW. Following the instruction of Instrument

operational manual provided by manufacturer,

analysis of Ni, Co, Cd, Cr, and Pb was carried

out using atomic absorption spectrophotometer

coupled with graphite furnace assembly. The blank

solutions proceeded the same way and are used

for the preparation of the calibration solutions and

for measurement of the blanks. Soil samples were

prepared in 3 depth of surface earth (5 cm, 50 cm,

and 100 cm). In order to quantitating analyze and

confirm the relationship among soil properties and

heavy metal content, the correlation analysis was

applied to dataset.

3. Results and discussion

The results of determination of heavy metals

in Isfahan’s industries regions show that the

concentration of Cr, Co, Ni, Cd and Pb in drinking

water and soil were very low and did not exceed

the permissible levels (TLV). In soil samples, all

of heavy metals (Cr, Co, Ni, Cd, Pb) have low

concentration in accordance to EPA and WHO

references. In addition, soil samples collected from

the land irrigated with waste water were higher

than well water . Heavy metals accumulated in

the surface soil layer may migrate into the deeper

layers, and consequently pose a threat of well water

contamination. The parameters of pollutants depend

on the type of soil and its properties. The mean of

concentration of Ni, Co and Cd in surface soil (5.23

± 0.22 , 8.42 ± 0.42, 0.35 ± 0.02) were higher than

deeper layers (2.15 ± 0.12 , 3.28 ± 0.19, 0.08 ±

0.01), but Pb and Cr were uniform in surface and

Table 2. temperature programming for the graphite atomizer of ET-AAS

Element Cd Co Cr Ni Pb

Drying 130 130 130 130 130

Ashing 300 800 1100 900 400

Atomization 1800 2300 2500 2400 2000

Table 3. Permissible limits of the metals in soil and water (FAO/WHO)

WHO Ni Co Cr Cd Pb

Soila2-40 0.1-50 1-180 0-0.2 1-200

Waterb70.0 80.0 50.0 3.0 10.0

a-1

b-1

Evaluation of heavy metals pollution in Isfahan; Shahnaz Teimoori

deeper layers of soil. Concentrations of Cr, Co, Cd

and Ni in waste water near industrial region (were

higher than well water and lead was not significant

effect (P<0.05). The dietary limit of metals in water

and soil is very important and permissible limits of

the metals in soil and water have reported by FAO/

WHO [20-24] (Table 3). Mean concentration of

Ni, Co, Cr, Cd and Pb in soil, well/drinking water

obtained in Table 4.

Many industries located near agricultural land in

Isfahan’s regions. Some of points (A, B) was near

to industries regions have higher concentration of

heavy metals than other points (C-H). Nickel is a

toxic metal that occurs naturally in environment.

Results of our study show that maximum

concentration of nickel was found in waste water

-1) and the minimum concentration in

well water and drinking water were obtained 37.43

-1-1.

The mean concentration of nickel in drinking

         

L-1   -1      -1,

respectively. Cobalt is an essential micronutrient

for man, animals, and plants for a range of

metabolic process. However, in any case the use

of cobalt supplementation has been associated with

toxic side effects such as cardiomyopathy. The

high concentration of cobalt in human as compare

       -1)

can be affected on nervous system, bones, liver,

Table 4. Mean concentration of metals in soil and water of Isfahan’s oil refinery regions (N=10)

Sample Average Metal Concentration a

Cr Ni Co Cd Pb

Waste Waterb95.24± 4.31 146.48± 7.12 185.48± 9.03 23.36 ± 1.33 11.64± 0.53

Well waterb28.35 ± 1.48 52.12 ± 1.86 68.53 ± 2.77 0.26 ± 0.01 1.08 ± 0.04

Soilc3.38 ± 0.17 3.47 ± 0.18 5.17 ± 0.28 0.13±0.006 2.19 ± 0.14

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

b-1

c-1

Sample Average Metal Concentration a

Cr Ni Co Cd Pb

Wastewater a377.3± 14.4 246.3± 11.8 299.7± 12.3 67.5 ± 4.2 94.1± 6.5

a-1

Fig. 2. Mean concentration of metals in well, drinking and waste water of Isfahan’s industries regions.

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

pancreases, teeth and causes blood diseases. Results

of our study show that maximum concentration of

        -1)

and the minimum concentration in well water and

   -1    -1). The mean

concentration of cobalt in well water, waste water

-1

L-1      -1 respectively. Cobalt

and nickel have a high concentration in waste

water as compared with WHO references. USEPA

drinking water standard for chromium and FAO

recommended the maximum limit for irrigation

-1. Results of chromium show that

maximum concentration was found in waste water

-1) and the minimum concentration in

-1-1).

The mean concentration of Cr in well water, waste

       -1, 377.3±

  -1      -1, respectively.

Speciation chromium in waste water showed that

the Cr (VI) has high concentration than Cr (III)

(C< 65%) and in well water had more less 10%.

Cadmium and lead have a high concentration in

waste water as compared with WHO references. In

waste water, maximum / minimum concentration

-1/ 24.4

  -1    -1 / 36.5± 2.2

-1), respectively. The mean of Cd and Pb in

well waters, drinking waters and wastewaters was

achieved (12.37 ± 1.33; 0.26 ± 0.01; 67.5 ± 4.2) and

(11.64± 0.53; 1.08 ± 0.04; 94.1± 6.5), respectively.

4. Conclusion

In this study, the concentration of heavy metals

such as Cr, Co, Cd, Pb, and Ni in soil, well water

and waste water in Isfahan’s industries regions

were analyzed. After digestion the soil and waste

water samples with microwave, the concentration

of heavy metals determined by ET-AAS. The

concentrations of Cr, Co, Cd, Pb and Ni in drinking

water and soil have low TLV with compared to

WHO/FAO references. But the same metals except

lead have high concentration in well water. Lead

concentration was not significant in samples

(P<0.05). Figure 1 showed that the A,B points have

higher concentration of heavy metals than other

points in Isfahan’s regions. The mean concentration

of Cr, Ni, Co, Cd, and Pb in well water were 95.24

± 4.31, 146.48 ± 7.12, 185.48 ± 9.03, 12.37 ± 1.33,

and 11.64 ± 0.53, respectively. Therefore, Cr, Co,

Cd, and Ni in well water from these regions can

probability cause pollution in environmental and

humans. In addition, the concentrations of such

elements in soils and well/drinking waters are less

Fig. 3. Mean concentration of metals in sampling point of waste water in Isfahan’s oil refinery regions.

Evaluation of heavy metals pollution in Isfahan; Shahnaz Teimoori

and near found in accordance to EPA and WHO

references, respectively. Therefore, the pollution of

heavy metals such as; Cr, Co, Cd and Ni in Isfahan

industrial regions can be diffused to well waters

and eluent waters and cause many problems in

plants and humans.

5. Nomenclature

DDW: double de-ionized distil water

WHO: Water Health Organization

6. Refrences

[1] L. Jarup, Impact of environmental pollution on

health, balancing risk, Br. Med. Bull., 68 (2003)

167-182.

[2] Agency for Toxic Substances and Disease Registry



chromium, and lead, (2004).

[3] National Health and Nutrition Examination Survey,

Atlanta centers for disease control (ACDC), GA

30333, (2010).

[4] Agency for Toxic Substances and Disease Registry



Atlanta, US department of public health and human

services (2005) 1-2.

[5] S. Uchida, T. Keiko, H. Ikuko, Soil-to-plant transfer

factors of stable elements and naturally occurring

     

Japan, J. Nucl. Sci. Technol., 4 (2007) 628-640.

[6] M. Abbas, P. Zahida, Muhammad Iqbal, M. Riazuddin,

S. Iqbal, A. Mubarik, R. Bhutto, Monitoring of

toxic metals (cadmium, lead, arsenic and mercury)

in vegetables of Sindh, Pakistan, Kathmandu

University, J. Sci. Eng. Technol., 2 (2010) 60-65.

[7] G. Amrita, S. Das, S. Dhundasi, K. Das, Effect of

garlic (Allium sativum) on heavy metal (Nickel

II and ChromiumVI) induced alteration of serum



Pub. health, 3 (2008) 147-151.



silica gel: a new solid sorbent for preconcentration

and determination of traces of cobalt (II) ion, Anal.

Chim. Acta, 569 (2006) 139-144.

[9] 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, Spec. Acta

A, Mol. Biomol. Spec., 12 (2004) 2897-2901.

[10] J. L. Manzoori, A. Bavili-Tabrizi, Cloud point

    

spectrometric determination of cobalt and nickel in

water samples, Microchim. Acta, (2003) 201-207.

[11] T. Sanders, Neurotoxic effects and biomarkers of

lead exposure: a review, Rev. Environ. health, 24

(2009) 15-46.

[12] M. Jakubowski, Low-level environmental lead

exposure and intellectual impairment in children,

the current concepts of risk assessment, Int. j.

Occup. Med. Environ. health, 24 (2011) 1-7.

[13] L. D. Wang, F. Y. Zhou, X. M. Li, L. D. Sun, X.

Song, Y. Jin, J. M. Li, Genome-wide association

study of esophageal squamous cell carcinoma in



PLCE1, Nat. Gen., 9 (2010) 759.

[14] Y. L. Liu, K. L. Luo, X. X. Li., X. Gao, R. X. Ni,

S. B. Wang, X. L. Tian, Regional distribution of

longevity population and chemical characteristics

of natural water in Xinjiang, China Sci. Total

Environ., 473, (2014), 54-62.

[15] A. H. Arias, J. Eduardo Marcovecchio, Continent

Derived Metal Pollution Through Time: Challenges

of the Global Ocean, Marine Pollution and Climate

Change, CRC Press, (2017) 107-125.

[16] M. Krishnamurthy, P. Ramalingam, K. Perumal, L.

P. Kamalakannan, J. Chinnadurai, R. Shanmugam,

K. Srinivasan, V. Venugopal, Occupational heat

stress impacts on health and productivity in a steel

industry in southern India. Safety and health at

work, (2017) 99-104.

       

and preconcentration using zirconium (IV) and

zirconium (IV) phosphate chemically immobilized



AAS, Talanta, 2 (2005) 537-542.

[18] J. Sunderman, F. William, M. Sidney Hopfer,

T. Swift, W. N. Rezuke, L. Ziebka, P. Highman,

B. Edwards, M. Folcik, H. R. Gossling, Cobalt,

chromium, and nickel concentrations in body

       

prostheses, J. Orth. Res., 7 (1989) 307-315.

[19] H. Shirkhanloo, A. A. Beigi, M. M. Eskandari, B.

Kalantari, Dispersive liquid-liquid microextraction



and speciation of chromium in human blood, J.

Anal. Chem., (2015) 1448-55.

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

[20] Singh S., M. Kumar, Heavy metal load of soil,

water and vegetables in peri-urban Delhi, Environ.

Monit. Assess., 120 (2006) 79-91.

[21] P. J. Li, X. Wang, G. Allinson, X. J. Li, X. Z. Xiong,

Heavy metals, J. Hazard. Mater., 161 (2009) 516.

[22] R. K. Yadav, B. Goyal, R. K. Sharma, S. K. Dubey,

P. S. Minhas, Post-irrigation impact of domestic

      

and ground water, a case study, Environ. Int. J., 28

(2002) 481-486.

[23] W. H. Liu, J. Zhao, Z. Ouyang, L. Söderlund,

G. Liu., Impacts of sewage irrigation on heavy

metal distribution and contamination in Beijing,

China., Environ. Int. J., 31 (2005) 805-812.

[24] Muchuweti, Maud, J. W. Birkett, E. Chinyanga, R.

Zvauya, Mark D. Scrimshaw, J. N. Lester, Heavy

metal content of vegetables irrigated with mixtures

of wastewater and sewage sludge in Zimbabwe:

implications for human health, Agriculture,

Ecosystems Environ., 112 (2006) 41-48.

[25] L. Schenk, S. O. Hansson, C. Rudén, M. Gilek,

Occupational exposure limits: A comparative study,

Reg. Toxicol. Pharm., (2008) 261-270.

[26] World Health Organization (WHO), Boron

in drinking-water: Background document for

development of WHO Guidelines for drinking

water quality, Geneva, (2009).

[27] S. Sarkar, A.Tanveer, K. Swami, D. Christopher,

B. Abdul, A. Vincent, H. Liaquat, History of

atmospheric deposition of trace elements in lake

sediments, J. Geophys. Res.: Atm., 11 (2015)

5658-5669.

[28] JI N. Kumar, H. Soni, R. N. Kumar, I. Bhatt,

Macrophytes in phytoremediation of heavy metal

contaminated water and sediments in Pariyej

Community Reserve, Gujarat, India, Turkish J.

Fish. Aqu. Sci., 2 (2008) 193-200.

[29] K. Mortazavi, M. Ghaedi, M. Roosta, M.

Montazerozohori, Chemical functionalization of

silica gel with 2-((3-silylpropylimino) methyl)

phenol (SPIMP) and its application for solid phase

extraction and preconcentration of Fe (III), Pb (II),

Cu (II), Ni (II), Co (II) and Zn (II) Ions.” Indian J.

Sci. Technol., 5 (2012) 1893-1900.

[30] H. Mizuguchi, T. Takahashi, A. Sasaki, S. Junichi,

Ultra-trace determination of lead (ii) in water using

electrothermal atomic absorption spectrometry

after preconcentration by solid-phase extraction to

a small piece of cellulose acetate type membrane



[31] S. Z. Mohammadi, T. Shamspur, M. A. Karimi,

E. Naroui. “Preconcentration of trace amounts of

Pb (ii) ions without any chelating agent by using

magnetic iron oxide nanoparticles prior to ETAAS



[32] D. A. Skoog, F. J. Holler, R. Stanley,

Crouch instrumental analysis, Belmont: Brooks/

Cole, Cengage Learning, 47 (2007).

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

1- Introduction

Nowadays, five major and hazardous pollutants

which can pollute and threaten drinking water,

groundwater, urban water, and bottled water are

known. The pollutants are arsenic, lead, fluoride,

chromium, and radioactive substances. Due to the

impossibility of biodegradation of arsenic in the

environment, it remains in contaminated water,

and thereby, it is considered as one of the most

hazardous pollutants in wastewaters and water

resources. In addition, the tendency of arsenic to

accumulate in the members of the body causes

dangerous diseases and cancers. The effects of

arsenic on the liver and nervous networks are

very prominent and cause a delay in mental

activity and anemia. In addition, arsenic enters

in the water, irrigated water, and environment

in various ways such as mining, printing, and

reproduction industries, petrochemical complexes,

and chemical industries or as a pollutant in their

effluent. According to available standards for

drinking water, the limit for arsenic is up to 10 ppm

Ahmad Ghozatlooa,*, Amir Zarei a,b and Mojtaba Arjomandi c,d

a Research Institute of Petroleum Industry, Tehran, Iran, Postal Box 14765-1376

b Department of Analytical chemistry, Payam Noor university, Kerman, Iran/ Department of Analytical chemistry Science and Research Branch, Islamic

Azad University, Tehran, Iran

c Department of Water Sciences and Engineering, Science and Research Branch, Islamic Azad University, Tehran, Iran/ Research Institute of Petroleum

Industry (RIPI), Tehran, Iran

d Department of Geophysics and Hydrogeology, Geological Survey and Mineral Explorations of Iran (GSI), Tehran, Iran

Synthesis and performance of graphene and activated carbon

composite for absorption of three-valance arsenic from wastewater

*Corresponding Author: Ahmad Ghozatloo

E-mail: ghozatlooa@ripi.ir

https://doi.org/10.24200/amecj.v2.i01.53

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

Received 4 Feb 2019

Revised form 28 Feb 2019

Accepted 14 Mar 2019

Available online 21 Mar 2019

Keywords:

Arsenic

Graphene

Activated carbon

Adsorption

Acidity of wastewater

A B S T R A C T

The presence of high levels of arsenic in the effluent is a major concern of human,

and the removal of it from the wastewater is hard and costly. The most common

techniques for removal of arsenic are membrane separation, ion exchange,

oxidation, and coagulation. All of these technologies eventually lead to the

separation of arsenic from wastewater and its accumulation among absorbent

materials, which are precipitated as sludge or extracted from liquid intermediate

phase. In this adsorption method, materials such as active alumina, active carbon,

titanium oxide, silicon oxide, and many natural and artificial elements are used.

Considering that active carbon is used as the most common arsenic adsorbent

in wastewater treatment processes, this study has been considered as the main

adsorbent and attempted to improve its surface properties by graphene nanosheets.

Thus, by adding 4.5 w.% graphene to the carbon structure, its porosity increases,

and the ion exchange behavior and surface load are corrected. In this research,

the effects of time process, concentration of arsenic, and adsorbent are evaluated

in different pH values. It has been observed that the maximum adsorption of

arsenic is 91.8%; in addition, when graphene is used, the rate of absorption of

Arsenic has increased about 5.2%, and the process time is shortened. In addition,

using graphene is cost-effective. It is also observed that the efficiency of the

adsorption process increases near neutral pH values; therefore, the adsorption

method by graphene/activated carbon composite in neutral cells can be used as

an additional method for industrial wastewater treatment.

Arsenic analysis in wastewater; Ahmad Ghozatloo, et al

Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 63-72

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

[1]. There are various methods for the adsorption

or removal of arsenic from contaminated water

sources, the most important of which are chemical

deposition [2], reduction by electron ultrafiltration

[3], ion exchange [4], and absorption process [5].

Among these approaches, the absorption method is

more cost-effective, efficient, and easy-to-absorb,

and extensive studies on the absorption of arsenic

by adsorption processes have been reported [7-5].

However, researches are looking for adsorbents

with a higher absorption rate, the identification of

an ideal adsorbent for the maximum absorption

of arsenic has not yet been suggested clearly.

Activated carbon has been used with the proper

properties as an efficient absorbent in treatment of

industrial wastewater for a Long time, especially

in the absorption of metal ions. In the meantime,

various technologies, including nanotechnology,

have increased the capacity of adsorbents used

to absorb more pollutants, including arsenic,

so that a new view has been opened in the field

of wastewater treatment. For example, carbon

nanotubes [8], graphene [9], graphene-oxide

[10], various graphene base materials, including

graphene hybrids [11] and graphene/metal oxide

nanocomposites [12], including nano-absorbents

which have been used in extensive researches,

and by using them, the best results have been

obtained. Moreover, no information is available

to use the adsorption of graphene/activated carbon

for removing arsenic from wastewaters. Graphene

oxide has shown good results in the removal of

some heavy metals from the effluent, which, in

its structure, oxygen acts as an absorption agent

for metal ions [13]. In graphene/activated carbon

composite, each of graphene and activated carbon

structures exhibits distinct effects on each other’s

performance. For example by considering the

effect of activated carbon on graphene behavior, it

can be admitted that the layer of graphene plate is

rolled onto activated carbon that not only prevents

the graphene from sticking together, but also

increases the porosity of the composite structure.

Consequently, it increases the specific surface of

adsorbents, which it is ideal target for sorbents.

On the other hand, graphene sheets, due to their

very small structures, act as a filler among the

active carbon structures and due to its conductive

behavior, and thereby, the absorption path in the

new structure of activated carbon is shortened.

It also facilitates the transfer of free electrons in

the composite structure and lowers its resistance.

This phenomenon is also the ideal goal of an

ideal adsorbent in sorption of ions [14]. In this

research, the graphene/activated carbon composite

synthesized as a porous adsorbent with a high

specific surface area is used for absorbing arsenic

from industrial effluent.

2. Experimental

2.1. Synthesis of Activated carbon/gra phene composite

absorbent

At First, graphene oxide has been obtained by

Hammers method with the mechanism of opening

of graphite layer sheets. After that, a double layer

dish with dilute sulfuric acid is washed, and while

the solution of sulfuric acid including graphite is

stirred, the temperature of the solution is reached to

0 °C using liquid cooling circulator. The amount of

2300 ml of sulfuric acid (98%) has been poured into

the reactor and mixed with 100 g of pure graphite

powder into the container, and the mixing operation

has been carried out for 30 minutes. Afterwards, the

amount of 300 g of solid potassium permanganate

powder is slowly added to the mixture during

6 hours, and the mixture is stirred for one hour

after completion. Then the temperature circulator

is increased to 40 °C, and after stabilizing the

temperature, the mixing operation continuous for

about three hours. For dilution, 500 ml of distilled

water is added with caution to the reactor, and the

circulator bleach and 3.5 liters of distilled water

are poured into a larger container, and then the

contents of the reactor are slowly transferred to a

larger container. Afterwards, the mixing operation

is carried out for one hour. The amount of 300 ml

hydrogen peroxide 30% has been slowly added to

the container, then mixing condition has continued

for 2 hours. Then 3 liters of chloride acid have

been added to 3 liters of distilled water separately.

Arsenic analysis in wastewater; Ahmad Ghozatloo, et al

Afterwards, the produced solution has been added

to the contents of the container. Then the process

continues for one hour. The stirrer has been turned

off, and the mixture has been subjected to the

intense ultrasound waves for 4 hours since the

opened plates do not adhere to each other. After

that, the container has been settled about eight

hours until the sediment is formed. Then from the

above part of the container, the produced solution

has been poured out, and the sediment contents

of the container are filtered. The strained cake is

transferred to a Chinese plant. Afterwards, the cake

is placed in a vacuum oven at 50 °C for two hours,

and then rinsed ultrasonically with distilled water

until neutral pH is achieved. After the neutralization

process, the powder formed is used as the graphene

oxide [15]. To prepare activated carbon, first 200 g

of powdered glucose is placed into a quartz tube.

The reactor is placed under nitrogen atmosphere

for 30 minutes. It is then gently warmed up to a

temperature of 350 °C and remained for 2 hours.

The glucose is carbonized under these conditions

and is colored as a black powder. In order to

increase the activated carbon efficiency, its surface

activation is carried out to perform a graphene

composite synthesis reaction under a two-step pre-

activation process. In the first step, at first, 10 g of

activated carbon powder is mixed with 20 g of zinc

chloride, and the mixed composite powder is added

to 300 ml of distilled water in a closed container.

Afterwards, the produced solution is exposed

to heat for 7 hours at 70 °C. During the heating

process, the water must not evaporate, and the

process is carried out in a dilute aqueous medium.

This action causes the activated carbon to become

more porous. Then, the mixture becomes smooth

with a filter paper, and the smooth mixture is dried

in an oven at 80 °C for 1 hour. The dried powder is

placed in a tubular quartz reactor, and the powder is

heated for one hour under neutral atmosphere while

temperature is equal to 400 °C. The powder has

been extracted from the reactor. Then the powder

has been poured into a one-molar chloride acid at

90 °C for 30 minutes. This has been carried out

to remove chloride from the remaining activated

carbon powder. The remaining mixture is filtered

and washed with warm distilled water several times

to remove remaining and additional chemicals. The

filter cake is dried in an oven at 65 ° C for 11 hours.

In the second step, 10 g of the carbon powder

obtained from the first step has been mixed with 30

g of potassium hydroxide, and the obtained mixture

has been placed in 300 ml of distilled water into the

container and brought to a temperature of 50 °C.

Then the mixture is mixed with alternating heat for

1 hour. The resulting mixture has been filtered with

filter paper. Afterwards, the filtered mixture has

been dried in an oven that its temperature is equal

to 80 °C for 1 hour. The dried powder is placed in a

tube quartz reactor and heated slowly at 700 ° C for

one hour under neutral atmospheres. The powder

has been brought out from the reactor. Afterwards,

it has been dried in an oven at 40 °C for one night.

Dried powder is a porous activated carbon that

is susceptible to participation in the graphene

composite structure. In order to synthesize the

active graphene / activated carbon composite, first

add 0.9 grams of dried graphene powder to 200

ml distilled water and add ultrasonic waves of 100

watts for a period of two hours, which appears as

a mixed mustard mixture. Then, the amount of 20

grams of activated carbon powder is slowly added

to the ultrasonic mixture for 3 hours. The mixture



evaporates. The remaining solids are introduced

into a quartz reactor formed in a tube, and under

a nitrogen atmosphere, it is slowly heated to 350

° C and left for 2 hours. The final product of this

reactor is the graphene/activated carbon composite

[16].

2.2. Study of structural properties of graphene/

activated carbon composite

In order to investigate the crystalline structure and

the phases present in the synthesized graphene/

carbon composite, X-ray analysis has been carried

out. In this study, a XRD spectrometer (Philips,

PW-1840) with a beam of 1.494 nm and a voltage

of 40 kV and a current of 30 mA has been used.

The spectrum obtained has been compared with

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

the Hammers graphene XRD. This comparison is

shown in Figure 1.

According to Fig. 1 (a), it is seen that the graphene

obtained from the Hammer’s process at 12.5

degrees has a sharp and narrow peak, which

indicates the crystalline structure of the graphene

oxide form, this means that the process of opening

graphite plates in the reaction of oxidation

with concentrated acid (Hammers process) is

successfully achieved. While in Figure 1 (b), the

peak has been shifted to a point of 26.5 degrees and

its intensity is very low. This criterion is a carbon-

crystalline structure with double bonds without the

presence of oxygenation groups, which has been

observed in pure graphene structure. As a result,

the process of making the graphene/activated

carbon composite, which has undergone a severe

heat stroke, causes the oxygen groups have been

removed from the composite structure. It also

shows that the synthesized composite structure is

free of any non-carbon bonding, in other words,

there is no additional contaminant in its structure.

In the following, a comparison of the two types of

graphite and synthesized composites is made, as

seen in Figure 2.

It is observed that the peaks of D and G in the area

of cm-1 of 1338 and 1611 cm-1 appear to be good

in this function respectively. The D-peak represents

structural defects that appear due to its presence

in destructive environments such as concentrated

(or s trong) acidic environments or the presence

of d i fferent operating groups on the graphene’s

structural surface, while the G-peak is due to the

grap h ite crystalline network produced by the

carbon bonds. Thus, the ratio of the intensity of the

D/G peaks is an indicator of the structural state of

graphene, which is equal to 0.88, as shown in Fig.

2a. This ratio indicates the presence of high oxygen

groups on the structure of the Hammers graphene,

whil e in Fig. 2b, this value is increased to 1.69

due to the elimination of oxygen’s groups of the

present graphene in the destructive environment.

Thes e results are also consistent with the XRD

anal y sis shown in Fig. 1. In order to study the

surf a ce properties of graphene/activated carbon

composite, the TEM image has been used, as seen

in Fig. 3. According to Fig. 3, it can be seen that the

Fig. 2. Raman spectrum: (a) Graphene (b) Graphene / activated carbon composite.

Fig. 1. XRD spectrum of graphene / activated carbon

composite

Arsenic analysis in wastewater; Ahmad Ghozatloo, et al

II BET device, the Japanese company BelJapan,

has been used. Preparation of samples is including

drying and degassing, which for this purpose, the

specimens should be heated in vacuum at 120 °C for

10 to 15 minutes for removing water vapor, carbon

dioxide, or other molecules that may occupy the

volume of the material cavities. Then the samples

cool down to the liquid temperature of the nitrogen

gas. Then the amount of nitrogen gas absorbed by

the composite or graphene structure is measured

by gradually increasing the relative pressure, and

its depletion rate is calculated by decreasing the

pressure at a constant temperature of 77 K. It has

been observed that in each case, with an increase in

relative pressure, the nitrogen uptake has increased,

and in the depletion mode, the same initial pattern

of absorbed nitrogen volume has been obtained.

The summary of the results is presented in Table 1.

According to the Table 1, graphene has shown an

increase in the specific surface area of activated

carbon by 87%. Also, the graphene composite with

Fig. 3. TEM image of graphene/active carbon composite.

layered structure of graphene nanosheet, which has

a micro-length, is well opened, and active carbon

particles are interacting. Small graphene layers are

randomly and irregularly distributed in activated

carbon particles.

Moreover, in circular shapes, in addition to carbon,

they also interact with each other, which have

created a structural network in activated carbon

and produced a total porosity. Moreover, this

phenomenon is due to a large amount of disruption

in the open graphene layers during the Hammers

process which is linked by functional groups

in the edges and structural defects of graphene

to activated carbon. The very narrow channels

created by the graphene plates inside the activated

carbon structure cause large structural porosity of

the composite to be obtained. To investigate the

structural porosity of synthesized composites, the

technique of nitrogen absorption and desorption

under different relative pressures has been used by

the BET method. In this research, the Belsorp mini

Table 1. pores status analysis based on BET analysis results.

Total pore

volumeMesoporous 

Average pore

diameter (nm)

Specific surface

area (m2 / g)

Isotherm absorption

typeStructure

0.373037.661Type I absorptionHammers graphene

2.4588.2982Type II absorptionActivated carbon

2.9195.61841Type IV absorptionGraphene composite

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

a specific surface area of 1841 m2/g exhibits a

very active surface structure that is very attractive

in the absorption region. In addition, the process

of synthesis of graphene composites has increased

the volume of activated carbon cavities up to 18%,

indicating an increase in the absorption capacity of

this structure. However, the size of the cavities is

not larger and, as a result, the number of each of

them is much larger. The presence of graphene in

the active carbon structure reduces the size of the

cavities, so that the average diameter of the cavities

in t h e composite is reduced b y 22%. In other

words, the hypothesis of the interaction between

grap hene and activated carbon on each other in

the composite structure is v isible from the point

of view of the positive effect of graphene on the

active carbon structure and graphene reduces the

size of the cavities and increases their number in

the activated carbon structure. Based on the results

of the structural analysis of synthesized composite,

which indicates the proper position of this structure

as a sorbent, it is further used to absorb arsenic in

water.

2.3. The evaluation system of absorbent performance

and process variables

In this study, a batch reactor system has been used

in a laboratory scale to carry out the process of

adso r ption and removal of arsenic in water, the

schematic illustration is shown in Fig. 3.

In accordance with Fig. 4, the system, which has

been used, consists of a double-headed reactor of

Pyrex with an internal volume of 300 cc, which is

an environment for an adsorption reaction. During

the absorption process, a circulator has been used

to transfer the required temperature and to maintain

the f low of the agent into the reactor’s second

wall. The reactor is equipped with a mechanical

agitator system that can control the speed of the

stirrer in different periods. At the end of the stirrer

rod, two parallel blades, with 2 cm in length, are

placed at an angle of 1 cm above the bottom of

the reactor, which is made of polymer and neutral,

with the aim of mixing the wastewater and the

lack of deposition of the adsorbent at the end of

the container is used during the absorption process.

Also, this system provides an opportunity to study

the rate of mixing speed in the absorption process.

To provide the required heating, a magnetic stirrer

equi p ped with an electric heater can also be

used . Arsenic adsorption process for two active

carbon adsorbents and graphene/activated carbon

composite for 200 cc wastewater containing three-

valence arsenic (Al3+) in water at 45 °C with an

abrasive stirrer 700 rpm has been carried out, and

their results have been compared with each other.

Thes e processes have been repeated at different

times and at different concentrations of arsenic in

water and different concentrations of adsorbent and

pH values. These values are presented in Table 2.

3. Results and discussion

Acco r ding to the variables defined, the arsenic

adsorption process is performed by two adsorbents

including active carbon and active carbon-graphene

composite in two pH values. In these experiments,

the amount of adsorbent is used, and the time of the

adsorption process with the initial concentration of

arsenic in the wastewater is changed in two levels.

Upon completion of the test, the amount of arsenic

in the wastewater is measured by atomic absorption

analysis with the PerkinElmer 2380 machine. The

amount of adsorption of arsenic after the adsorption

proc e ss is calculated by the following equation

(Eq. 1).

Fig. 4. Schematic of the absorption reactor system.

Arsenic analysis in wastewater; Ahmad Ghozatloo, et al

qe=(C0-Ce).V/m (Eq.1)

where qe is the amount of absorption after reaching

the equilibrium state with unit mg/g, C0 and Ce are

the initial and final concentrations of arsenic in the

wastewater, which their units are mg/L, obtained

by atomic absorption analysis and V is the volume

of wastewater used per Liter, and m is the absorbent

weig h t used in grams. Then based on the initial

conc e ntration of arsenic in the wastewater, the

efficiency of arsenic adsorption is calculated. The

absorbent absorption efficiency is obtained using

the following equation (Eq. 2):

% Removal=(C0-Ce)/C0 ×100 (Eq.2)

Table 2 summarizes the number and conditions of

abso r ption experiments. For more precision and

the possibility of repeatability of the experiments,

each experiment has been repeated three times,

and i ts mean value as absorption efficiency has

been calculated and reported. In addition, Table 3

summarizes the results of arsenic adsorption under

various laboratory conditions.

According to Table 3, it is generally observed that

the a dsorption rate in activated carbon/graphene

composites is higher than of activated carbon, so

that under the same conditions due to the positive

effect of graphene on porosity. The total amount of

adsorption increased from 6.6% to 9.3%, and the

highest amount of arsenic adsorption occurred when

using 200 mg graphene/activated carbon composite

in 1 2 0 minutes for effluent with concentration

of 1 0 0 mg which is 42.4%. It is observed that

incr e asing the concentration of arsenic in

wastewater decreases the amount of absorption due

to the presence of more arsenic in the wastewater

Table 2. The absorption Process Variables.

High Level of variationLow variation levelNon-dependent variableNumber of variables

200100concentration of absorbers (mg)1

12060time of adsorption2

200100Amount of absorbent (mg As / L)3

63pH4

Table 3. The Summary of the results of arsenic adsorption under various laboratory conditions

Absorbent

type

The

amount of

adsorbent

(mg)

Time of

absorption

(minute)

Initial

concentration

(mg As/L)

Absorption

Test

Conditions

pH=6 pH=3

Absorption

rate (%)

Secondary

concentration

(mg As/L)

Absorption

rate (%)

Secondary

concentration

(mg As/L)

Activated carbon

100

60 100 AC1 79.2 79.2 74.4 74.4

200 AC2 77.1 154.2 74.0 148.0

120 100 AC3 80.3 80.3 74.2 74.2

200 AC4 79.7 159.4 76.4 152.8

200

60 100 AC5 86.4 86.4 80.2 80.2

200 AC6 85.9 171.8 83.4 166.7

120 100 AC7 84.5 84.5 78.4 78.4

200 AC8 86.6 173.2 83.3 166.6

Composite

100

60 100 AC/G1 83.8 83.8 77.6 77.6

200 AC/G2 82.2 164.4 79.1 158.2

120 100 AC/G3 85.3 85.3 80.4 80.4

200 AC/G4 83.1 166.2 79.9 159.8

200

60 100 AC/G5 91.8 91.8 85.5 85.5

200 AC/G6 90.7 181.4 87.6 175.2

120 100 AC/G7 92.4 92.4 86.1 86.1

200 AC/G8 91.6 183.2 88.5 176.9

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

and the creation of mass transfer resistance in its

tran s fer to the absorbent level. In this case, by

comparing the absorbance value for active carbon,

the same phenomenon is observed, as the amount

of adsorption decreases by about 2.5%. Therefore,

the amount of arsenic adsorption by active carbon

with the presence of arsenic in large concentrations

is inversely proportional, and it can be used as a

supplementary method in adsorption. It can be seen

that the presence of graphene in the activated carbon

structure due to electron exchange in the sites at the

edges and structural defects of graphene humors

incr e ases the absorption performance. However,

the time of the absorption process does not have

any significant effects on it, based on this study,

if it is required to absorb less than 1% of arsenic

in wastewater by using graphene/activated carbon,

the time of absorption must be increased twice. In

addition, if it is required to absorb less than 1% of

arsenic in wastewater by using activated carbon,

the time of absorption must be increased 2.3 times.

As a result, graphene has increased the adsorption

rate, which has accelerated the absorption process,

and has a positive effect on the economy of this

process. Therefore, due to the negligible difference

and the very little effect of absorption time with

the p resence of graphene, the absorption time at

60 mi nutes as an optimal point of the process is

suggested. By changing the amount of acidity of the

effluent from 6 to 3, the empirical values obtained

in Fig. 2 are reported.

Acco r ding to Fig. 5, it is observed that with

incr e asing pH in all experiments, the amount of

adso r ption increases. Generally, it is seen that

the reduction of the pH of the effluent is strongly

infl u enced by the amount of absorption due to

the c ompetition of adsorption of arsenic in the

acid i c environment. In addition, it is observed

that in lower pH values, the amount of adsorption

decr e ases, but the intensity varies in different

conditions. When only activated carbon adsorbent

is u s ed, the greatest effect of pH is on AC3

adso r ption conditions, which changes 6.1% of

absorption, whereas when composite absorbent is

used, the most effect of pH is on AC/G7 adsorption

conditions, of which 6.3 units change the absorption

perc e ntage. In general, the maximum amount of

arse n ic adsorption decreased by 6.3%, which is

related to dilute arsenic concentrations when 200

mg of composite absorbent is taken at 60 and 120

minu t es. Therefore, it is noted that the time of

adsorption process has no significant effect on the

amount of arsenic adsorption. To better evaluate the

effect of time on adsorption, absorption processes

Fig. 5. Comparison of the effect of pH on arsenic removal under various laboratory conditions.

Arsenic analysis in wastewater; Ahmad Ghozatloo, et al

are compared with each other over a period of 60

minutes. According to Table 4, it is observed that

in t h e same condition, the presence of graphene

increases the amount of arsenic absorption.

Acco r ding to Table 4, the presence of graphene

in neutral pH (pH = 6) has a greater effect on the

absorption rate due to the intrinsic effect of more

grap h ene porosity on the total of the adsorbent.

Moreover, the lack of ionic resistance in adsorption

of arsenic could also point to the phenomenon of

favo r able spatial inhibition between graphene

sheets in neutral media due to the negative charge

found in the graphene agent groups of Hammers.

That way, by increasing the pH of the environment,

the p resence of positive ions in the wastewater

decreases, and the tendency to converge graphene

plat e s in the composite weakens. As a result,

adsorption of arsenic by composite adsorbent with

less resistance and more surfaces by graphene is

done. This subject occurs with the same intensity

in t h e 120-minute adsorption period. Due to the

presence of graphene in the structure of activated

carbon, the effect of absorbing time is insignificant.

In a d dition, due to the structural nature of the

adso r bent and the low concentration of arsenic,

better adsorption is there in the process. Therefore, it

is observed that with the presence of less adsorbent,

the greatest effect of pH in the adsorption process

is due to the presence of graphene in the adsorbent

structure which increases the absorption to about

1.4 t imes. That is, graphene greatly enhances

the e ffect of the pH of the wastewater, in other

words, when the composite absorbent is used, the

sensitivity of the adsorption process to higher pH

changes should be controlled with greater precision

and be limited to higher pH.

4- Conclusion

Acti v ated carbon as one of the most suitable

and e fficient adsorbents in adsorption of arsenic

in i n dustrial effluents has a good performance,

so t h at it can separate about 86.6% of arsenic

from wastewater during 120 minutes. Because

the a dsorption process carried out by activated

carbon is related to porosity and ion exchange, it is

attempted to upgrade these parameters by changing

its s tructure. For this purpose, the graphene

stru c ture of Hammers, which has a very high

porosity and anionic surface charge, as a modern

idea is used in this research. It has been observed

that the presence of graphene in the adsorbent

structure has caused a significant increase in the

amount of adsorption of arsenic, so that in optimum

cond i tions, the adsorption rate increased up to

91.8%. On the other hand, the absorption time of

more than 60 minutes have not had any significant

effects on absorption, and this process causes the

more economical due to requiring of shorter time

for balancing the maximum absorption. Moreover,

by observing the effect of wastewater pH, graphene

perf o rmance has been improved at higher pH

values due to the force of dissolved ion potential

difference at the rate of adsorption of arsenic by

composite absorber. Therefore, it can be controlled

by adjusting the pH of wastewater, and the use of

corr e cted graphene structures easily controls the

absorption process and increases the efficiency of

abso r ption. Also, it has been observed that with

incr e asing arsenic concentration, the absorbent

performance of the composite is weakened. Due to

the sensitivity of the presence of arsenic in released

wastewater, these types of adsorbents are suitable

for final purification and dilute wastewater.

Table 4. The Increasing adsorption of arsenic by the presence of graphene in the adsorbent structure.

amount of adsorbent

(mg)

Initial concentration

(mg As L-1)

Time of absorption

(min)

pH=3

Increase in

absorption (%)

pH=6

Increase in

absorption (%)

100 100 60 3.2 4.6

100 200 60 5.1 5.1

200 100 60 5.3 5.4

200 200 60 4.2 4.8

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

5. References

[1] M. A. P. Cechinel, A. A. U. de Souza, Study of arsenic

adsorption onto activated carbon originating from

cow bone, J. Clean. Prod., 65 (2014) 342–349.

[2] J. H. Park, Y. S. Han, J. S. Ahn, Comparison of arsenic

co-p r ecipitation and adsorption by iron minerals

and the mechanism of arsenic natural attenuation

in a mine stream, Water Res., 106 (2016), 295–303.

[3] L. R. Molinari, P. Argurio, Arsenic removal from

water by coupling photocatalysis and complexation-



Res., 109 (2017) 327-336.

[4] B. Pakzadeh, J. R. Batista, Surface complexation

mode l ing of the removal of arsenic from ion-

exch a nge waste brines with ferric chloride, J.

Hazard. Mater., 188 (2011) 399–407.

[5] D . Santra, M. Sarkar, Optimization of process

variables and mechanism of arsenic (V) adsorption

onto cellulose nanocomposite, J. Mol. Liquids, 224

(2016) 290–302.

[6] O. P. Chen, Y. J. Lin, W. Z. Cao, C. T. Chang, Arsenic

remo v al with phosphorene and adsorption in

solution, Mater. Lett., 190 (2017) 280–282.

[7] A. Sigdel, J. Park, H. Kwak, P. Pyung-Kyu, Arsenic

removal from aqueous solutions by adsorption onto

hydrous iron oxide-impregnated alginate beads, J.

Ind. Eng. Chem., 35 (2016) 277–286.

[8] A .A.H. Izzeldin, S.M. Bice, J. Catherine, O.N.

Vincent, Adsorption studies of aqueous Pb(II) onto

a sugarcane bagasse/multi-walled carbon nanotube

composite, Phys. Chem. Earth 66 (2013) 157–166.

[9] R . Soni Dericks, P. Shukla, Data on Arsenic(III)

remo v al using zeolite-reduced graphene oxide

composite, Data in Brief, 22 (2019) 871-877.

[10] G. Zhao, X. Ren, X. Gao, X. Tan, J. Li, C. Chen,

Y. Huang, X. Wang, Removal of Pb(II) ions from

aqueous solutions on few-layered graphene oxide

nanosheets, Dalton Trans., 40, (2011) 945–952.

[11] L. Cui, Y. Wang, L. Gao, L. Hu, L. Yan, Q. Wei, B.

Du, EDTA functionalized magnetic graphene oxide

for removal of Pb(II), Hg(II) and Cu(II) in water

trea t ment: adsorption mechanism and separation

property, Chem. Eng. J., 281 (2015) 1–9.

[12] Z. Goharibajestani, A. YudaYürüm, Effect of

tran s ition metal oxide nanoparticles on gas

adsorption properties of graphene nanocomposites,

Appl. Surface Sci., 475 (2019) 1070-1076.

[13] G. Zhao, J. Li, X. Ren, C. Chen, X. Wang, Few-

laye r ed grapheme oxide nano-sheets as superior

sorbents for heavy metal ion pollution management,

Environ. Sci. Technol., 45 (2011) 454–462,

[14] C. Zheng, X. Zhou, H. Cao, G. Wang, Z. Liu,

Synt h esis of porous graphene/activated carbon

comp o site with high packing density and large

   

material, J. Power Sources, 258 (2014) 290–296.

[15] M. Sohail, M. Saleem, S. Noor Saeed, A. Afridi, M.



synt h esis of graphene oxide for capacitors

applications, Modern Elec. Mater., 3 (2017) 110-

116.

[16] A. Ganesan, M. M. Shaijumon, Activated graphene-

deri ved porous carbon with exceptional gas

adsorption properties, Micropor. Mesopor. Mater.,

220 (2016) 21-27.

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

Introduction

The most Pollutants such as volatile organic

comp ounds (VOCs, BTEX)and semi-volatile

comp ounds (SVOCs, Di-nitrotoluene) release to

air and environment by various industrial processes

and human activity such as petrochemical facilities,

moto r vehicles, metal processing/finishing

indu stries, gas stations, and energy sectors.

Tran sport-derived emissions of volatile organic

comp ounds (VOCs) have decreased owing to

stricter controls on air pollution. The high fraction

of volatile chemical products (VCP) emissions is

consistent with observed urban outdoor and indoor

air. VCP contribute fully one-half of emitted VOCs

in i ndustrialized cities. Based on previous study,

the toluene concentration was the most predominant

among all the targeted compounds in air. So, removal

of t oluene from air is very important [1-5]. These

comp ounds (VOCs) are associated with allergies

and adverse respiratory effects [6] and some of them

have been classified as carcinogenic to humans

(ben zene, formaldehyde) by the International

Agen cy for Research on cancer[7] . A complex

Cobra Jamshidzadeh a and Hamid Shirkhanloo b,*

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

b,Research Institute of Petroleum Industry, West Entrance Blvd., Olympic Village, P.O. Box: 14857-33111, Tehran, Fax: +98 21 48251

A new analytical method based on bismuth oxide-fullerene

nanoparticles and photocatalytic oxidation technique for

toluene removal from workplace air

*Corresponding Authors: Hamid Shirkhanloo

Email: hamidshirkhanloo@gmail.com

https://doi.org/10.24200/amecj.v2.i01.55

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

Received 28 Nov 2018

Revised form 4 Feb 2019

Accepted 5 Mar 2019

Available online 29 Mar 2019

Keywords:

Toluene

Air removal

Bismuth oxide nanoparticles

Bulky fullerene nanoparticles

UV-photocatalytic

Solid gas phase extraction

A B S T R A C T

A new sorbent based on mixture of bismuth oxide-fullerene nanoparticles

(Bi2O3-NF) was used for degradation/removal of toluene from workplace

and artificial air by UV-photocatalytic oxidation method (UV-PCOM).

By set up of pilot, standard gas of toluene was generated with difference

conc entrations, and then was passed through UV lamp-glass quartz cell

accessory(UV-GQC) by SKC pump at optimized flow rate. Following the UV

irradiation, the electrons and holes can undergo redox reactions with toluene

on the Bi2O3 surface that lead to the formation of toluene intermediates and

toluene. Toluene and intermediates was physically and radically absorbed

on the 200 mg of NF at room temperature and then, desorbed from it at 185

OC before determined by GC/FID. In optimized conditions, the adsorption

capa city and removal efficiency of NF were obtained 212 mg g-1 and

more than 95%, respectively. The chemically absorption mechanism of

toluene on NF was mainly obtained due to radically group of NF (OHo,

COo) with methyl of toluene (CH2

o) and physically adsorption depend on

characterization of NF. In addition the flow rate and temperature had highly

impact on NF for removal efficiency and absorption capacity of toluene

from workplace and artificial air.

Analytical method for toluene removal from air; Cobra Jamshidzadeh, et al

Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 73-86

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

comb ination of physicochemical and biological

phenomena takes place to finally convert pollutants

into innocuous compounds (mostly CO2, H2O and

biom ass)[8].The accumulation of VOCs is the

greatest problem in air atmospheric pollutions with

cars or industrial activity. The BTEX pollutants

(ben zene, toluene, ethylbenzene and xylenes)

gene rated in air by gasoline combustion in car

engines and caused a risk to human health[9]. The

BTEX have a carcinogens effect in humans. They

readily volatilized and distributed over large regions

of a ir and have important role in photochemical

oxidants and organic aerosols[10]. Among various

types of VOCs, toluene is one of the most commonly

used substances in industry and commerce as a

solvent in paints, siliconesealants, many chemical

reac tants, rubber, printing ink,adhesives (glues),

lacquers, leather tanners, and disinfectants[11, 12].

Most of VOCs are regarded as toxic compounds

for human beings and the environment. symptoms

asso ciated with exposure to VOCs include eye

irri tation, nose and throat discomfort, headache,

allergic skin reaction, nausea, fatigue, or dizziness,

nerv ous system effects, liver toxicity, cancer[13,

14] . If inhaled or contacted, toluene can cause

derm atitis (dry, red, cracked skin) and damage

the nervous system and kidneys[12, 15]. The 8-h

time -weighted average (TWA) for occupational

expo sure to toluenein accordance with ACGIH,

OSHA , NIOSH methods is respectively 50,

200 and 100 ppm. Therefore, toluene emission

cont rol has become more stringent. Growing

conc erns on exposure to toxic air pollutants has

led to intensive search for the best available

tech nology for remediation of air pollutants[16,

17]. A number of physical, chemical and biological

tech nologies such as membrane separation[14]

ads orption[18], catalytic oxidation[19] and

adva nced oxidation[20] have been developed to

remove VOCs successfully. The control of toluene

emis sion is often accomplished by catalytic

oxidation or adsorption. The adsorption process is

widely used as a simple and effective operation[21].

Adso rption of VOCs by activated carbon (AC)

has proven to besustainable, environmentally

friendly, economical and efficient which makes it

the most commonly used technique[22]. Toluene

removal by adsorption is the traditional method

for cleaning air contaminants [23-25]. However,

the use of adsorbents just transfers pollutants

from the gaseous phase to the solid phase and

causes a disposal and regeneration problem[15].

Many studies have been done to remove toluene

usin g carbon adsorbent such as activated

carb on fibers (ACFs)[22], NaOCl oxidized

carb on nanotubes[26], Zeolite[15],Nano-

grap hene modified by ionic liquid[27] .

Buck minsterfullerene(C60) a hydrophobic

mole cule comprise a class of nanomaterials that

are made of a newly discovered allotrope of carbon

and composed of 60 carbon atoms arranged in a

hollow spheres, ellipsoids, or tubes spherical shape,

has gained wide application in many industries,

incl uding biomedical technology, electronics,

opti cs, and cosmetics[28-30]. In recent years,

advanced oxidation processes have been considered

as a way to pollute organic pollutants. These

methods are based on the production of highly active

species such as hydroxyl radicals (OH0) that can

oxidize a wide range of organic pollutants. Among

the advanced oxidation processes, heterogeneous

phot ocatalytic are used as a successful method

for the analysis of organic pollutants[31-33].

Degr adation of volatile organic compounds

such as, o-xylene, n-hexane, n-octane, n-decane,

methylcyclohexane and 2,2,4-trimethylpentane in

the gas phase by heterogeneous photocatalysis with

titanium dioxide/ultraviolet light was achived at 52-

62OC. in this way, devices based on heterogeneous

photocatalysis do not need flame for VOC oxidation,

this will allow it to be installed safely even in areas

vuln erable to fire and explosion[34, 35]. In this

study, the UV-PCOM based on Bi2O3-NFwas used

for efficient removal of toluene from air. The Bi2O3/

UV irradiation increased the removal efficiency of

toluene from air by chemically adsorption of NF.

Expe rimental parameters such as concentration,

UV i rradiation, temperature, the value of Bi2O3-

NF, flow rate, contact time, desorption, absorption,

and repeatability were studied and optimized.

Analytical method for toluene removal from air; Cobra Jamshidzadeh, et al

The performance of the proposed method was

evaluated.

2. Experimental

2. 1. Instrumental:

Gas chromatography (GC) was used for

dete rmination of toluene in air (Agilent,

Neth erland). The FID detector was selected for

toluene analysis in air/gas. The polyethylene tubes

(PET) are simple devices that introduce a pure air

stre am from electro air cleaner (EAC, Canada,

mode l HEPA 600M) into bags. Adjusted valves

are used to control of gas flow rate from Germany.

For sampling, the air bags, septum port and air

sampling apparatus were used. GC equipped with

a split/splitless injector, FID, and a column coated

with cross-linked polydimethylsiloxane gum

(50 m × 0.2 mm id.). For determining of toluene

with GC, The temperature of injector and detector

was adjusted to 200°C and 2700°C, respectively.

The temperature of oven was tuned from °C to

40°C which was held for 10 min. Hydrogen as the

carrier gas was used at a flow rate of 1.0 mL min-1

with split ratio of 1:100. The different volumes of

glas s vials (10-200 mL, Aldrich, Germany) with

air tight cap (PTFE) were used in batch or static

syst em. The polyethylene tubes and bags were

used as a transport and storage of air in static/

dyna mic system. TGS 2180 (China) and Dräger

Pac 3500 (Lübeck, Germany) detectors were used

for continuous measurement of H2O vapor and

O2 c oncentrations in gas fluid, respectively. The

TGS detector has high sensitivity to water vapor

and its conductivity depends on absolute humidity

(0.7~150 gm-3). Preheat of tubes and bags caused to

capture water droplets. The toluene evaporated from

cham ber accessory, mixed with purified air and

introduced to bags. For validation of methodology,

the concentration of toluene in polyethylene bags

was determined by GC-MS before and after passed

thro ugh Bi2O3-NF. The quartz glass tube (QGT,

10 cm) as a column sorbent was used for Bi2O3-

NF. In this study, QGT with 0.4 cm diameter and

10 c m length was filled with 200 mg of Bi2O3-

NF. The gas tight syringes (SGE) were used for

sampling of toluene and injection to GC. In this

study, toluene generation system, QGT, PET, bags,

electric power supply accessory (50-280 VAC, 10A,

20-800 oC, Italy), pneumatic valves (Germany) and

Ar gas were used for evaluation of toluene removal

from air. The accuracy of results was achieved by

injecting a standard concentration of toluene in the

chamber accessory before determined by GC-FID/

GC-MS.

2.2. Reagents and solutions

All reagents with high purity and analytical grade

were purchased from Merck and sigma Aldrich

(Darmstadt, Germany). All aqueous solutions were



cm-1) from Milli-Q plus water purification system

(Mil lipore, Bedford, MA, USA). The analytical

grad e of toluene solution was purchased from

Sigm a Aldrich, Germany (CAS N: 108-88-3,

99.8%). For calibration of toluene, the approximate

concentrations of toluene in methanol were prepared

by 0.1, 0.2, 0.3, 0.4, 0.5, 1.0, 2.0, and 5.0% (v/v).

The analytical grades of other reagents such as,

HNO3, HCl, methanol, ethanol and acetone were

prepared from Merck (Germany). Bismuth nitrate

(Bi (NO3).5H2O), sorbitol and distilled water used

for the preparation of Bi2O3 nanoparticles. Bismuth

nitrate (CAS N: 383074) and sorbitol (CAS N: 50-

70-4 ) were purchased from Sigma Aldrich. The

solutions were freshly prepared and stored just in

a fridge (4 °C) to prevent decomposition. All the

laboratory glassware and plastics were cleaned by

soaking in nitric acid (10%, v/v) for at least 24 h

and then rinsed with deionized water before use.

2.3. Synthesis bismuth oxide and fullerene

nanoparticles

Bism uth oxide nanoparticles (BONPs) were

prep ared by special solid dispersion evaporation

tech nique (SDAT) with carrier solutions such as

sorb itol and flame sprays pyrolysis technique

(FSP T) by organodimethicone (ODIM). By

SDAT Synthesis, 5 g of solid bismuth nitrate [Bi

(NO3).5H2O] dissolve in carrier solutions (5 ml)

and stirred for 20 min at room temperature followed

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

by sonication at 25 ºC in an ultrasonic bath (40 kHz

and 100 W). The mixture was diluted with 10 mL

of distilled water and put on heater magnet stirrer

plate for 30 min. The pH of sample solution was

optimized up to 7 and no precipitation was occurred

during processes. The oven provided programmable

heat ing up to 90–110 ºC for 50 min. Then dark

brown sediment was formed after the evaporation

of water. After 1 hour yellow sediment was formed

in 550–600 ºC and nano particles is decomposed at

800 -1200 ºC. In order to obtain pure BONPs and

remove the metal nanocatalysts, the product was

stirred in 18% HCl solution for about 16 h at an

ambient temperature. Then, the sample was washed

repe atedly (10N) with deionized water until the

solution became neutral. The treated product was

finally dried in oven at 100 ºC. So, bismuth nitrate,

sorbitol and distilled water used for the preparation

of Bi2O3 nanoparticles medical grade by proposed

procedure. For synthesis of fullerene (NF), fullerene

soot (FS) was purchased from Sigma-Aldrich and

pure fullerene (NF) was achieved with activated

carbonand silica gel (TEM size: 30-100 nm) [36].

The pure fullerene (C60) from fullerene soot (FS)

was done by two methods. By first procedure,

a So xhlet extractor with toluene was used for

separation of light and heavy fullerenes (Fig. 1).

The electric arc was used for producing of FS with

low purity up to 7%. The second way was obtained

by column chromatography with stationary phase

and mobile phase of activated carbon/ silica gel and

chlorobenzene, respectively.

2.4. Characterization

The morphology of the mesh sorbent Bi2O3 and NF

was examined using scanning electron microscopy

(SEM , Phillips, PW3710, Netherland) and

tran smission electron microscopy (TEM, CM30,

Philips, Netherland). The nanoparticle powder of

Bi2O3 is dissolved in water or ethanol with ultrasonic

bath and after drying, was prepared for TEM in

scal e of 50-100 nm. The elemental composition

of t he samples was tested by energy dispersive

X-ray microanalyser (EDX, QuanTax 200, Rontec,

Germ any) which was attached to SEM. X-ray

diffraction (XRD) patterns for Bi2O3 nanoparticles

were recorded by a GBC MMA diffractometer

      

oper ating at 35.3 kV and 30 mA. FT-IR 8400

(Kyo to, Japan); UV–vis spectrophotometers

Scinco S-2100 (SCINCO, Twin Lakes, WI, USA),

NMR Jeol 90 MHz (JEOL Ltd., Tokyo, Japan),

and rotary evaporator (Heidolph Laborota 4000,

Schwabach, Germany) were used for nanofullerene

(NF) characterization.

2.5. Removal Procedure

The concentration of toluene vapor in pure air was

Fig. 1. The schema of light and heavy fullerenes

Analytical method for toluene removal from air; Cobra Jamshidzadeh, et al

prep ared by pilot chamber (Fig. 2). The toluene

vapor was generated by and mixed with pure air

(210 mL of O2 per L; 2.5 mL of H2O per L) at 25oC.

This mixture was restored in polyethylene bag (5

Lit) and toluene was determined by GC-MS and

GC-FID. Based on producer, in bath scale set up,

10 mL of standard solutions of toluene (40-100 mg)

was convert to vapor gas and mixed to pure air and

then pass through silica gel and Bi2O3 nanoparticles

with flow rate of 500 mL min-1 at 10 min which was

irradiated by UV in quartz glass tube (QGT). Then,

toluene and intermediates was absorbed on NF by

physically and radically formation. Finally, toluene

and intermediates desorbed from NF at 185OC

befo re determined by GC/FID. For validation of

meth odology, GC-MS and spike of sample was

used . This method can be applied for toluene

removal from artificial and workplace air.

3. Results

In this research, Bi2O3-NF was used for efficient

removal of toluene from air. The Bi2O3 based on UV

irradiation can be increased the removal efficiency

of t oluene from air by radically adsorption. The

characterization of Bi2O3/NF such as TEM, SEM,

XRD, XRD and IR was prepared. The important

parameters include, toluene concentration, intensity

of UV irradiation, temperature, the mass of Bi2O3-

NF, flow rate, time and repeatability were studied

and optimized.

3.1. TEM, SEM, XRD and IR

The results of synthesis for Bismuth oxide

nano particles have been obtained in a series

of s canning electron microscope (SEM) and

transmission electron microscopy (TEM) images.

It was clarified that the size of nanoparticles are

obtained below 100 nm. The TEM and SEM images

of Bi2O3 have been demonstrated in figure 3 (a, b).

SEM and TEM of fullerene nanoparticles (NF) was

shown in figure 4(a, b) which was between 50-100

nm. The XRD of Bi2O3 and NF was shown in figure

5 a and 5b, respectively. The IR of NF (C60) was

shown in figure 6.

3.2. The effects of humidity

The concentration of toluene vapor in pure air was

prepared at 25oC (210 mL of O2 per L; 2.5 mL of

H2O per L). This mixture was restored in 5 Li of

polyethylene bag. Finally, toluene vapor in pure air

was removed from air by UV-PCOM method. By

procedure, the effects of humidity on adsorption

capacity of Bi2O3-NF in QGT were examined in

different humidity (10-60%). The value of humidity

in the pilot chamber was adjusted by the water

tank valve by auto electronic system in present of

silica gel. By increasing of humidity more than

40%, the removal efficiency of Bi2O3-NF was

Fig. 2. The pilot of toluene vapor generator in pure air and adsorption procedure

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

Fig. 3a. TEM picture of Bi2O3Fig. 3b. SEM picture of Bi2O3

Fig. 4a. TEM picture of NF

decreased (Fig. 7). The Previous study showed

that the trap device packed with silica composite –

multi walled carbon nanotubes (MSN-MWCNTs)

prepared based on sol–gel technique was used

for evaluation of volatile organic compounds at

20% humidity. Increasing of humidity may be

reduced the adsorption active sites on NF which

was occupied by water (-OH). On the other hand,

the nanoparticles of NF stick together with water

molecules increase in size and decrease of surface

Fig. 4b. SEM picture NF

area. All examinations were achieved by toluene

concentration (40 mg L-1), flow rate (500 mL min-

1), temperature (25oC), and 200 mg of Bi2O3-NF.

In optimized condition, the 20% humidity had low

effects on toluene removal from air less than 5%.

Also, the results showed us, the humidity had lower

effect than temperature.

3.3. The effect of toluene concentration

By optimizing conditions, the toluene removal

Analytical method for toluene removal from air; Cobra Jamshidzadeh, et al

from air based on Bi2O3-NF was studied in different

toluene concentration from 10-100 ppm (mg L-1).

The high surface area in NF based on UV lamp-

glass quartz cell accessory (UV-GQC) caused to

increasing of the adsorption capacity for toluene

removal from air. At high concentration of toluene,

the Bi2O3-NF can be acted as a favorite sorbent.

The optimum of toluene concentration for removal

efficiency (>99%) with 200 mg of Bi2O3-NF, NF,

Bi2O3 was achieved, 42.4 mg L-1, 20.6 mg L-1

Fig. 5a. XRD spectra of NF

Fig. 5b. XRD spectra of Bi2O3

Fig. 6. The IR spectra of NF

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

and 2.3 mg L-1 in 25oC, respectively. The results

showed, in optimized concentration, the Bi2O3-

NF had more adsorption capacity and removal

efficiency than others.

3.4. The effect of temperature

The temperature has a main factor for removal

efficiency of toluene from air by Bi2O3-NF. As

prevent to condensing toluene, the special thermal

accessory was used in pilot chamber for heat

controlling up to 115°C. The column of QGT was

used at below 45oC. The effect of temperature was

OC. The results showed us,

the absorption recovery of Bi2O3-NF was depended

to temperature. Desorption of toluene from Bi2O3-

NF was occurred at 185oC. In optimized conditions,

the removal recovery for toluene based on Bi2O3-NF

was more than NF up to 45oC (Fig. 8). Sone et al

showed that the adsorption of toluene was decreased

by increasing temperature. Increasing temperature

more than 50oC had negative effects on removal

efficiency of Bi2O3-NF and had more effected on

humidity. In this study, the adsorption capacity of

Bi2O3-NF and NF has obtained 212 mg g-1 and 99.6

mg g-1, respectively. Other parameters such as, the

surface area, flow rate, kind/ porosity/ source/ size

sorbent and chemical and physical adsorption can

be affected on removal of toluene from air. The

low adsorption capacity of nanosorbents related to

greater amounts of amorphous structure with low

surface area or increasing of temperature.

3.5. The effect of sorbent mass

The amounts of Bi2O3-NF (1:1) as a sorbent in the

range of 20 to 300 mg were tested on the recoveries

of toluene removal from air at 25oC. It was found

that 220 mg of Bi2O3-NF was sufficient for

quantitative recoveries of toluene removal from air.

Extra mass of Bi2O3-NF had no significant effect

on the efficient removal of toluene vapor in air. So,

200 mg of Bi2O3-NF was selected as an optimized

mass sorbent by UV-PCOM. Also, the Bi2O3 and

NF and Bi2O3-NF had maximum recovery up to

5.1% and 48.4% and more than 95%, respectively.

These results confirm that the radically group of

NF (OHo, COo) with methyl of toluene (CH2o) had

important role for removal of toluene in present of

Bi2O3 by UV-PCOM.

3.6. The effect of flow rate

The flow rates were optimized in order to obtain

the maximum recovery by proposed method. So,

the effect of different flow rates between 100 to

1000 mL min-1 was examined by Bi2O3-NF at room

temperature. The flow rate was measured by a digital

rotameter in input and output of QGT in optimized

conditions. The results showed us, the removal

efficiency and adsorption capacity of Bi2O3-NF

Fig.7. The effects of humidity on toluene adsorption by silica gel/ Bi2O3-NF

Analytical method for toluene removal from air; Cobra Jamshidzadeh, et al

was decreased in more than 550 mL min-1 of flow

rate. So, 500 mL min-1 of flow rate was selected as

optimum flow rate for removal of toluene in air.

Higher flow rate was significantly decreased the

adsorption recovery of Bi2O3-NF. Based on results,

the maximum of toluene adsorption by exterior and

interior sites of NF was obtained at less than 500

mL min-1. Figure 9 show the effects of difference

flow rate on the removal efficiency and adsorption

capacity in optimized conditions.

3.7. Method Validation

Due to obtained Results, the Bi2O3-NF was

selected as a novel sorbent for removal of toluene

vapor from air. By proposed method, a mixture of



by pilot, storage in PE bag (5 L). Then, the mixture

of toluene in artificial air moved to Bi2O3-NF in

present of argon gas as a carrier gas. The different

standard of toluene (mg) in air was validated by

high sensitive and accurate GC-FID/GC-MS before

using by UV-PCOM. Since no certified reference

Fig. 8. The effects of temperature on toluene adsorption and desorption from Bi2O3-NF

Fig. 9. The effects of flow rate on toluene removal by Bi2O3-NF and NF

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

material (CRM) for toluene in air are currently

available, the spiked of toluene concentration (10-

100 ppm) were used for validation of proposed

method. At optimized conditions in 5 and 10

minute, 20 ppm and 40 ppm of toluene vapor in

air was almost removed by Bi2O3-NF, respectively

(bag 5 L). The efficient recovery of spiked samples

is satisfactorily reasonable which indicates the

power ability of UV-PCOM based on Bi2O3-NF for

removal of air toluene. After thermal desorption of

Bi2O3-NF in QGT, the toluene concentration was

on-line determined by GC-FID. The validation of

methodology was confirmed using GC-MS (Table

1, 2).

4. Discussion

Volatile organic compounds (VOCs) are released

from various sources such as chemical processing

industries involved with the manufacturing,

handling, and the distribution of paints, lubricants,

and liquid fuels and are unsafe for human health are

known to have and environmental functions[37].

The numerous VOC treatment technologies have

emerged, such as incineration, condensation,

biological degradation, absorption, adsorption, and

catalysis oxidation. One of the common techniques

to monitor BTX in ambient air is the use of a

sorbent/solvent for the trapping and extracting of

VOCs from air or gas[38]. In this study, the toluene

removal from air was investigated based on mixture

of bismuth oxide-fullerene nanoparticles (Bi2O3-

NF) by UV-photocatalytic oxidation method (UV-

PCOM). The obtained results showed that flow

rate and temperature had highly impact on NF

for removal efficiency and absorption capacity of

toluene from air. Many researchers investigated

on toluene removal from air based on various

absorbents. The removal of toluene from air

through Nano-graphene modified by ionic liquid

(NG-IL) was studied. In this study the effect of

different conditions such as; toluene concentration,

humidity, and temperature on the adsorption were

investigated. The results showed the adsorption

Table 1. Method validation based on by spike of toluene concentration in artificial air by Bi2O3-NF/GC-FID (mg L-1)

Tolene aBag of pilot Spike of toluene Results b Recovery (%)

1.0 0. 93 ± 0.04 1.0 1..79 ± 0.05 96.2

5.0 4.58 ± 0.27 5.0 8.89 ± 0.46 97.1

10.0 9.43 ± 0.53 5.0 14.19 ± 0.65 101.2

15.0 14.39 ± 0.75 10.0 22.54 ± 1.23 94.6

20.0 19.70 ± 0.96 10.0 28.57 ± 1.33 98.2

25.0 24.65 ± 1.14 15.0 40.11± 2.16 102.7

a (Floe rate 500 mL min-1, Peak Area of GC-FID, 200 mg, T=45oC)

b (Mean of three determinations ± confidence interval, P = 0.95; n = 5)

Table 2. Comparing of Bi2O3-NF, Bi2O3 and NF for removal of toluene from artificial air by GC-FID/GC-MS (mg L-1)

Sorbent* Bag Added GC-FID a GC-MS aGC-FIDRecovery (%) GC-MS Recovery (%)

NF 5.0 ----- 2.34± 0.02 2.45± 0.02 46.8 49.0

5.0 4.53± 0.03 4.78± 0.04 43.8 46.6

10.0 6.68± 0.04 7.09± 0.05 43.4 46.4

Bi2O3-NF 5.0 ----- 4.88± 0.05 4.93± 0.06 97.6 98.6

5.0 9.71± 0.09 9.77± 0.10 96.6 96.7

10.0 14.95± 0.15 14.64± 0.16 101.1 97.1

Bi2O35.0 ----- 0.74± 0.03 0.77± 0.04 1.5 1.5

5.0 1.43± 0.07 1.51± 0.05 1.4 1.5

10.0 2.24± 0.12 2.33± 0.09 1.5 1.6

a (Mean of three determinations ± confidence interval , P = 0.95; n = 5)

* (500 mL min-1 air flow rate, 200 mg, T=45oC)

Analytical method for toluene removal from air; Cobra Jamshidzadeh, et al

capacity was decreased by raising the sorbent

humidity above 50 percent and the toluene capture

capacity for NG-IL was 126 mg g-1 which was

lower than Bi2O3-NF [27]. By UV-photocatalytic

oxidation method, the capacity of toluene

absorption with Bi2O3-NF was 212 mg g-1 which

was depended to UV-photocatalytic oxidation.

Lillo-Ródenas showed that the removal percentage

for toluene also may depend on porosity and the

surface chemistry of adsorbent. They showed that

adsorption capacities for benzene and toluene was

obtained 34 g per 100 g activated carbon(AC) and

64 g per 100 g, respectively which is lower than

Bi2O3-NF by UV-PCOM [39]. Surface chemistry

of activated carbon has an important role on the

removal of aromatic compounds in air because it

affects both electrostatic and dispersive interactions

between adsorbents and adsorbates [40]. In

proposed method, the chemically absorption of

toluene on NF mainly obtain due to radically group

of NF (OHo, COo) with methyl of toluene (CH2o).

Rezaei et al. have been used as complex system

of nano-particles of titanium dioxide on exposing

them by ultraviolet radiation. The results showed

titanium dioxide nanoparticles when subjected to

ultraviolet radiation ,exhibit strong oxidizing and

regenerative properties and can be used to remove

toluene vapors in high concentrations but it need

more time for adsorption process and titanium

dioxide nanoparticles is expensive as compare to

carbon compounds [41]. In addition, the use of a

suitable adsorbent according to the type of sorption

can be helped for removal toluene from air. Ichiura

at el. has suggested a sorbent based on zeolite or

activated carbon as a photocatalyst bed to improve

the efficiency of adsorption with higher recovery

[42].

Shojaee showed that ZSM-5 has a porous surface

with surface area of 356.4 m2 per gram. That

after the calcination at temperature of 450°c it

decreased to 332.5m2 per gram. The results of the

photocatalytic degradation process showed that

the best performance of ZSM-5/TiO2 bed was

at concentration of  ppm, so that was able to

remove  toluene vapors which was lower than

Bi2O3-NF [43,44]. According to obtained results,

removal of toluene from air based on Bi2O3-NF /

UV-PCOM was very rapid and absorption capacity

increased up to 212 mg per gram. Rezaee et al.

studied on the potential of MnO/GAC and MgO/

GAC composites for toluene adsorption from

air stream. They showed that, by increasing inlet

toluene concentration from 100 to 400 ppm, the

breakthrough time of MgO/GAC and MnO/GAC

was decreased [45]. So, the proposed method based

on Bi2O3-NF had many advantages such as, high

efficiency, simple, low cost for toluene removal

from air as compared to other methods.

5. Conclusions

In this study, the removal of toluene from air was

obtained based on Bi2O3-NF and UV-PCOM.

By procedure, many advantages such as, high

efficiency, high capacity, low cost, simple and fast

adsorption was achieved. In optimized conditions,

toluene concentration, Bi2O3-NF mass, temperature

and flow rate were evaluated. The capacity of

sorbents, recovery, and removal efficiency of

Bi2O3-NF, Bi2O3 and NF was studied by CG-FID

and GC-MS. Based on the results, the recovery of

Bi2O3-NF was more than Bi2O3 and NF sorbents.

Also, the maximum adsorption of toluene was

achieved with 200 mg of Bi2O3-NF by flow rate

of 500 mL min-1 (450C). Thermal accessory was

used for toluene desorption from Bi2O3-NF at 180

oC. Due to characteristics of Bi2O3-NF based on

physically and radically adsorption, toluene was

efficient removed from air by proposed method.

6. References

[1] W. T. Tsai, Toxic volatile organic compounds (VOCs)

in the atmospheric environment: Regulatory aspects

and monitoring in Japan and Korea, Environ., 3

(2016) 23.

[2] M.A. Bari, W.B. Kindzierski, Ambient volatile

organic compounds (VOCs) in communities of the

Athabasca oil sands region: Sources and screening

health risk assessment, Environ. Pollut., 235 (2018)

602-614.

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

[3] B.C. McDonald, J.A. de Gouw, J.B. Gilman, S.H.

Jathar, A. Akherati, C.D. Cappa, J.L. Jimenez,

J. Lee-Taylor, P.L. Hayes, S.A. McKeen,

Volatile chemical products emerging as largest

petrochemical source of urban organic emissions,

Sci., 359 (2018) 760-764.

[4] Z. Cheng, B. Li, W. Yu, H. Wang, T. Zhang, J. Xiong,

Z. Bu, Risk assessment of inhalation exposure to

VOCs in dwellings in Chongqing, China, Toxicol.

Res., 7 (2018) 59-72.

[5] L. Zhong, F.-C. Su, S. Batterman, Volatile organic

compounds (VOCs) in conventional and high

performance school buildings in the US, Int. J.

Environ. Res. Public Health, 14 (2017) 100.

[6] J.C. Lerner, E. Sanchez, J. Sambeth, A. Porta,

Characterization and health risk assessment of

VOCs in occupational environments in Buenos

Aires, Argentina, Atmospheric. Environ., 55 (2012)

440-447.

[7] I.A.f.R.o. Cancer, IARC monographs on the

evaluation of carcinogenic risks to humans, agents

     

Retrieved from http7/monographs. Iarc, fr/eng/



[8] A.J. Wheeler, S.L. Wong, C. Khoury, J. Zhu,

Predictors of indoor BTEX concentrations in

Canadian residences, Health Rep., 24 (2013) 11.

[9] S.J. Lawrence, Description, properties, and

degradation of selected volatile organic compounds

detected in ground water, a review of selected

literature, 2006.

[10] X. Xu, P. Wang, W. Xu, J. Wu, L. Chen, M. Fu,

D. Ye, Plasma-catalysis of metal loaded SBA-15

for toluene removal: comparison of continuously

introduced and adsorption-discharge plasma

system, Chem. Eng. J., 283 (2016) 276-284.

[11] W.K. Boyes, M. Bercegeay, L. Degn, T.E. Beasley,

P.A. Evansky, J.C. Mwanza, A.M. Geller, C.

Pinckney, T.M. Nork, P.J. Bushnell, Toluene

inhalation exposure for 13 weeks causes persistent

changes in electroretinograms of Long–Evans rats,

Neurotoxicol., 53 (2016) 257-270.

[12] Y. Li, J. Miao, X. Sun, J. Xiao, Y. Li, H. Wang,

Q. Xia, Z. Li, Mechanochemical synthesis of Cu-

BTC@ GO with enhanced water stability and

toluene adsorption capacity, Chem. Eng. J, 298

(2016) 191-197.

[13] C.Y.H. Chao, C. Kwong, K. Hui, Potential use of

a combined ozone and zeolite system for gaseous

toluene elimination, J. Hazard. Mater., 143 (2007)

118-127.

[14] M. Salar-García, V. Ortiz-Martínez, F. Hernández-

Fernández, A. de Los Ríos, J. Quesada-Medina,

Ionic liquid technology to recover volatile organic

compounds (VOCs), J. Hazard. Mater., 321 (2017)

484-499.

[15] D. Romero, D. Chlala, M. Labaki, S. Royer, J.-

P. Bellat, I. Bezverkhyy, J.-M. Giraudon, J.-F.

Lamonier, Removal of toluene over NaX zeolite

exchanged with Cu2+, Catalysts, 5 (2015) 1479-

1497.

[16] Y.J. Tham, P.A. Latif, A.M. Abdullah, A. Shamala-

     

removal by activated carbon derived from durian

shell, Bioresour. Technol., 102 (2011) 724-728.

[17] NIOSH manual of analytical methods, NIOSH,

(1987).

[18] H. Sui, H. Liu, P. An, L. He, X. Li, S. Cong,

Application of silica gel in removing high

concentrations toluene vapor by adsorption and

desorption process, J. Taiwan Ins. Chem. Eng.,

(2017).

[19] Z. Sihaib, F. Puleo, J. Garcia-Vargas, L. Retailleau,

C. Descorme, L. Liotta, J. Valverde, S. Gil, A.

Giroir-Fendler, Manganese oxide-based catalysts

for toluene oxidation, App. Cat. B Environ., 209

(2017) 689-700.

[20] Z. Pengyi, L. Fuyan, Y. Gang, C. Qing, Z. Wanpeng,

A comparative study on decomposition of gaseous

toluene by O3/UV, TiO2/UV and O3/TiO2/UV, J.

Photochem. Photobiol., 156 (2003) 189-194.

[21] S. Wang, H. Sun, H.-M. Ang, M. Tadé, Adsorptive

remediation of environmental pollutants using

novel graphene-based nanomaterials, Chem. Eng.

J., 226 (2013) 336-347.

[22] G.B. Baur, O. Beswick, J. Spring, I. Yuranov, L.

Analytical method for toluene removal from air; Cobra Jamshidzadeh, et al



VOC removal from diluted streams: the role of

surface functionalities, Adsorption, 21 (2015) 255-

264.

[23] A. Faghihi-Zrandi, M. Akhgar, Volatile Organic

Compounds (VOCs) in the Ambient Air Of

Concentration Unit of Sar-Cheshmeh Copper

Complex, Environ. Sci. Technol., 18 (2016) 23-31.

[24] G. Quijano, A. Couvert, A. Amrane, G. Darracq,

C. Couriol, P. Le Cloirec, L. Paquin, D. Carrié,

Potential of ionic liquids for VOC absorption and

biodegradation in multiphase systems, Chem. Eng.

Sci., 66 (2011) 2707-2712.

[25] F.G. Shahna, F. Golbabaei, J. Hamedi, H. Mahjub,

H.R. Darabi, S.J. Shahtaheri, Treatment of benzene,

toluene and xylene contaminated air in a bioactive

foam emulsion reactor, Chinese.Chem. Eng., 18

(2010) 113-121.

[26] F. Su, C. Lu, S. Hu, Adsorption of benzene, toluene,

ethylbenzene and p-xylene by NaOCl-oxidized

carbon nanotubes, Colloids Surface A, 353 (2010)

83-91.

[27] H. Shirkhanloo et al, Nobel Method for Toluene



Nano-Graphen, Iranian J. Occp. Health, 6 (2015)

1-5.

[28] M.R. Wiesner, G.V. Lowry, P. Alvarez, D. Dionysiou,

P. Biswas, Assessing the risks of manufactured

nanomaterials, Environ. Sci. Technol., 40 ( 2006)

4336-4345.

[29] Y. Li, Y. Wang, K.D. Pennell, L.M. Abriola,

Investigation of the transport and deposition of

fullerene (C60) nanoparticles in quartz sands under



(2008) 7174-7180.

[30] A.G.C. A.V. Rode, E.G. Gamaly, S.T. Hyde,

B. Luther Davie, carbon based magnetism, an

overview of the magnetism of metal free carbon-

based compounds and materials, Elsevier, (2006)

463-482.

     

water and air: advanced oxidation processes

(AOPs)-principles, reaction mechanisms, reactor

concepts, John Wiley & Sons, (2003).

[32] G.Y.M. Al-Nour, Photocatalytic degradation of

organic contaminants in the presence of graphite



particles, Nablus: An-Najah National University,

(2009).

[33] H.I. De Lasa, B. Serrano, M. Salaices, Photocatalytic

reaction engineering, Springer, 2005.

[34] C. Montalvo-Romero, C. Aguilar-Ucán, M.

Ramirez-Elias, V. Cordova-Quiroz, A Semi-Pilot

Photocatalytic Rotating Reactor (RFR) with

Supported TiO2/Ag Catalysts for Water Treatment,

Molecul., 23 (2018) 224.

[35] U.L. Rochetto, E. Tomaz, Degradation of

volatile organic compounds in the gas phase

by heterogeneous photocatalysis with titanium

dioxide/ultraviolet light, J. Air Waste Manag.

Assoc, 65 (2015) 810-817.

[36] H. Keypour, M. Noroozi, A. Rashidi, An improved

      

fullerene soot with activated carbon, celite, and

silica gel stationary phases, J. Nanostruct. Chem.,

3 (2013) 45.

[37] K. Patil, S. Jeong, H. Lim, H.-S. Byun, S. Han,

Removal of volatile organic compounds from

air using activated carbon impregnated cellulose

acetate electrospun mats, Environ. Eng. Res.,

(2018).

[38] X. Zhang, B. Gao, A.E. Creamer, C. Cao, Y. Li,

Adsorption of VOCs onto engineered carbon

materials: A review, J. Hazard. Mater., 338 (2017)

102-123.

[39] M. Lillo-Ródenas, D. Cazorla-Amorós, A. Linares-

Solano, Behaviour of activated carbons with

different pore size distributions and surface oxygen

groups for benzene and toluene adsorption at low

concentrations, Carbon, 43 (2005) 1758-1767.

[40] F. Villacañas, M.F.R. Pereira, J.J. Órfão, J.L.

Figueiredo, Adsorption of simple aromatic

compounds on activated carbons, J. Colloid.

Interface. Sci, 293 (2006) 128-136.

[41] H. Ichiura, T. Kitaoka, H. Tanaka, Removal of indoor

pollutants under UV irradiation by a composite

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

TiO2–zeolite sheet prepared using a papermaking

technique, Chemosphere, 50 (2003) 79-83.

[42] Rezaee A., Pourtaghi Gh. H., Khavanin A., Saraf

Mamoori R., Hajizadeh E., Vali pour F., Elimination

of toluene by Application of ultraviolet irradiation

on TiO2 nano particles photocatalyst, Mil. Med., 9

(2007) 217-222.

[43] H. Asilian Mahabady, A. Khavanin, M. Nakhaei

pour, H. irvani, S. Aresoomandan, H. Shojaee fareh

  

removal of toluene vapour by titanium dioxide

nanoparticles immobilized on ZSM-5 zeolite, Iran

Occp. Health J., 15 (2018) 17-25.

  

Zeolite and Cooper Oxide Nanoparticles-

   

for Polluted Air BTX Removal, Iranian J. Health

Environ., 5 (2012).

[45] F. Rezaei, G. Moussavi, A.R. Riyahi Bakhtiari,

Y. Yamini, Toluene adsorption from waste air

stream using activated carbon impregnated with

manganese and magnesium metal oxides, Iranian J.

Health Environ., 8 (2016) 491-508.