1. Introduction

Volatile organic compounds (VOCs) enter the

environment through various sources, leaving

severe environmental and health impacts

[1].

The production of industrial wastewater is the

main origin of VOCs which is considered as a

negative aspect of industrial activity, exerting

several adverse effects on the environment and

human health

[2-6]. Volatile organic compounds

are one of the most widely used materials

in the production of refrigerants, plastics,

adhesives, paints, and petroleum products

[3,

5, 7-12]

. Benzene and toluene are regarded

as the most hazardous materials in the volatile

organic compounds family and regarding their

importance, a considerable amount of literature

has been published on the issue of benzene and

toluene potential adverse effects on health

[13-

16]

. According to the international agency for

research on cancer

[17], benzene is categorized as

group 1 (carcinogenic to humans) and Toluene as

group 2B (quietly carcinogenic to humans). What

we know about the adverse effects of benzene and

Toluene is largely based on previous studies which

have proved that the common adverse effects

of these organic compounds is neurotoxicity

including drowsiness, headache, tremor, coma and

dizziness

[16, 18-20]. Benzene exposure has been

reported to increase the risk of various cancers

including leukemia and hematopoietic cancers

A Review, Methods for removal and adsorption of volatile

organic compounds from environmental matrixes

Shahnaz Teimoori

, Amir Hessam Hassani

b,*

Mostafa Panahi

and Nabiollah Mansouri

PhD student of environmental engineering, Faculty of Natural Resources and Environment,

Science and Research Branch, Islamic Azad University, Tehran, Iran

Department of environmental engineering, Faculty of Natural Resources and Environment,

Science and Research Branch, Islamic Azad University, Tehran, Iran

Department of environmental engineering, Faculty of Natural Resources and Environment,

Science and Research Branch, Islamic Azad University, Tehran, Iran

Department of environmental engineering, Faculty of Natural Resources and Environment,

Science and Research Branch, Islamic Azad University, Tehran, Iran

ABSTRACT

The volatile organic compounds (VOCs) have toxic effects on human

health and environmental matrices. So, determination and removal of

VOCs from the environmental samples such as water, wastewater and air

are very important as they exert toxic effects on human. Many chemical

techniques such as; analytical methods for sorbents (extraction, adsorption),

sole gel method, pervaporation, regenerative catalytic oxidation (RCO),

recuperative catalytic oxidation (CO), adsorptive concentration-catalytic

oxidation, photocatalytic oxidation (PCO), ozonation-catalytic oxidation

and non-thermal plasma-catalytic oxidation, have been used for removal

and reduction of VOCs from different matrices. This review study has

been conducted to collect the adsorbents and applied chemistry methods

which have been recently used in different works for the elimination of

VOCs from air and water samples.

Keywords:

Volatile organic compounds,

Chemistry and biochemistry method,

Removal,

Adsorption,

Water and air

ARTICLE INFO:

Received 6 Mar 2020

Revised form 5 May 2020

Accepted 30 May 2020

Available online 30 Jun 2020

Research Article, Issue 2

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

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

Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

Corresponding Author: Amir Hessam Hassani

Email: ahh1346@gmail.com

https://doi.org.

[15, 21]. It has been also recognized that benzene

and Toluene affect skin, eyes and respiratory

tract by inducing irritation

[22-25]. Increased

threatening impacts of VOCs increase health

and environment concern and therefore, there is

a crucial need to develop effective strategies to

remove them. Several attempts have been made

to eliminate or recover VOCs from wastewater;

for example, distillation is commonly used,

regardless of azeotropes formation or high energy

consumption

[6, 7, 10, 12, 26-29]. Hitherto, a

number of approaches including adsorption

[30-

32]

, condensation [33], incineration [34, 35] and

thermal oxidation

[36] have been established

to eliminate VOCs from the environment.

Treatment methods that have been established

for VOCs removal are as follows: air stripping,

adsorption, advance oxidation, distillation,

anaerobic/aerobic biological treatment and the

technology of membrane

[27, 29, 37-42]. Many

researchers have also applied pervaporation with

nonporous membranes such as silicon rubber-

coated PP to remove aromatic compounds from

water sources

[43-45]. Moreover, a large body

of studies has taken the advantage of membrane-

based air stripping (MAS) process by the means

of microporous hollow ﬁber contactors which

is very effective in the treatment of aqueous

efﬂuents containing VOCs

[46-56]. In the context

of catalytic oxidation (one of the used techniques

for VOCs removal), many researchers have

focused on catalysts including noble metals (e.g.

, TiO

, CeO

, MnOx), nonmetal oxides (e.g.

SiO

), zeolites (e.g. ZSM, MCM, NaY) [57-62]

and carbon derivatives

[63, 64]. However, metal

oxides that are in charge of VOCs elimination

are mostly derivatives of elements distributed in

groups III-B through II-B of the periodic table

such as Ti, Cu, Mn, Al, Ce, Co, Fe and so on

[65-

67]

. Despite extensive attempts toward VOCs

removal, conducted technologies have, to some

extent, shortcomings and limitations. This paper

aims to review techniques used for VOCs removal

and discuss their advantages/disadvantages and

ﬁnally, focus on introduced solutions to improve

the process of VOCs elimination.

2. Data sources

In this review, we used information such as

journal articles, statistical data and conferences/

seminars papers as our data source. Surﬁng

in scientiﬁc websites and databases including

Google Scholar and Web of Science was a major

way of accessing valuable information and related

articles. Therefore, it was important to search at

least one of related key words which are included

in either titles or abstracts of papers and are as

follows: “VOCs removal”, “Catalytic oxidation”,

“Adsorbents” and “Nanomaterials”. It was also

crucial for papers to contain one or more of the

aforementioned keywords to be embodied in this

review.

3. Experimental procedures and methods

3.1. Sorbent Methods

The analytical methods for sorbents based on

extraction and adsorption (chemical and physical)

were used for VOCs removal from water and

wastewater samples. Recently, the phenyl

sulfonic acid (PhSA) modiﬁed carbon nanotubes

(CNTs) were presented for benzene removal

(BR) from waters. For separation process, the

PhSA@CNTs based on the dispersive micro solid

phase extraction method (D- SPE) was used

for BR from water. The main mechanism was

achieved by the polar– or – electron donor–

acceptor interactions between the benzene and

SO3H /C6H5 group of CNTs surface

(Fig. 1).

According to the procedure, 10 mg of CNTs@

PhSA nanostructures was added to 5 mL of water

samples with different benzene standard solution

(0.1--10 mg L

-1

) in GC vial. After shacking

and centrifuging (3500rpm), the CNTs@PhSA

sorbent separated from water samples and ﬁnally,

its concentration was determined by static head

space gas chromatography mass spectrometry

(SHS-GC-MS)

[68]. The mechanism based on

CNTs@PhSO

H was obtained with – stacking

between aromatic chain and S=O bond of

CNTs@PhSO

H (Fig. 2).

Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al

The graphene based materials (GBMs) have been also

used as a new technology in different ﬁelds of science

specially in the environmental chemistry. The GBMs

adsorbent was used for the removal of VOCs with

high adsorption capacity and cost-effectivity through

various functionalization processes on the surface.

The intermolecular forces of GBMs with the gaseous

pollutants caused gas adsorption. The strength of the

interaction of GBMs with VOCs depended on surface

area/properties, pore volume/size of the GBMs.

The GBMs showed the excellent adsorption for the

removal of VOCs. Among the different graphene

structures, GO and rGO have mostly used for the

VOC removal from waters

[69]. The various models

of the GO structures are shown in

Figure 3 which

was used for VOCs removal in different matrices.

Hofmann and Holst ﬁrst introduced graphite oxide

and then Ruess et al designed a graphite oxide

structure based on a wrinkled carbon sheet. Scholz

and Boehm showed that the carbon sheet replaced by

carbonyl and hydroxyl. Nakajima and Matsuo used

two carbon layers linked to each other by sp

CeC

bonds with carbonyl and hydroxyl groups. Lerf et al

suggested a graphite oxide based on the unoxidized

rings of benzene and that a wrinkled region of alicyclic

6- membered ring ethers is distributed randomly in a

ﬂat aromatic region. Szabó et al., showed a carbon

network structure

[70-73].

Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

Fig. 1. Benzene extraction from waters based on CNTs@PhSA by D--SPE

method

Fig. 2. Mechanism of extraction of benzene with CNTs@PhSO3H

benzene, toluene, and xylene (BTX) are the

major members of VOCs pollutions. These

VOCs are preferably adsorbed on hydrophobic

surfaces as compared to hydrophilic surfaces

[74-75]. The previously results showed, the GO

may exhibit less adsorption capacity for aromatic

VOCs. Yu et al showed for 50 ppm benzene,

the adsorption capacities for GO and rGO were

obtained 216.2 and 276.4 mg g

-1

, respectively.

The rGO sorbent has a hydrophobic property

with enhanced tendency (- bonds), increasing

the adsorption capacity of VOCs relative to GO

sorbents. In addition, the surface areas for rGO

and GO were achieved 292.6 m

-1

and 236.4

-1

, respectively and due to high surface

area of rGO, the adsorption capacity of VOCs

was increased

[69, 74, 75]. Szczniak et al

showed that the high surface area of GBMs and

GO caused to improve the benzene adsorption

capacities for OMC. The incorporation of

GO with OMC / KOH increased the surface

area from 740 m

-1

to 1370 m

-1

. Also, the

pore volume of OMC from 0.61 increased to

1.06 cm

-1

after the formation of GO/OMC.

Finally, adsorption capacities for benzene were

obtained 633 mg g

-1

and 750 mg g

-1

for OMC

and GO/OMC, respectively

[76-77]. GO - MOF-

5 was used for the removal of benzene vapor

from air with capacity of 251 mg g

-1

[78]. Due

to high porosity of MOFs, they cannot retain

small molecules under ambient conditions. So,

the GO/MOF-5 composite was prepared using

varying proportions of GO, such as 1.75 wt%,

3.5 wt%, 5.25 wt%, and 7 wt%

(Fig 4).

Fig. 4. Adsorption-desorption isotherms for graphene

oxide/metal organic framework-5 (GO/MOF-5)

for benzene [78]. MG (1–4) represents GO/MOF-5

composite with 1.75%, 3.5%, 5.25%, and 7% of GO

in MOF-5.

The GO and rGO was used for the removal of

toluene by Kim et al. The – bonds, hydrophobic

and electrostatic interaction with toluene led to

the absorption of toluene on GO / rGO surfaces

(Fig. 5). Different types of GBMs such as graphene

platelets (GP), rGOMW, and KOH activated

rGOMW (rGOMWKOH)) were analyzed for the

toluene adsorption

[79].

Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al

Fig. 3. Various models of the GO structure [70].

Aldehyde and ketone compounds are the most

carbonyl VOCs which can be considered as

sources of the environment contamination. GBMs

can efﬁciently remove the carbonyl compounds

from environment. For indoor formaldehyde

removal, amino functionalized graphene sponge

(G/S) or G/S decorated with graphene nanodots

(G-GND/S) were used by Wu et al. G-GND/S

with high amine groups on surface as compared to

G/S caused a high interaction with formaldehyde

molecules

(Fig 6). The results showed that

the adsorption capacity of GGND/S and G/S

were achieved 22.8 mg/g

-1

and 7.5 mg/g

-1

for

formaldehyde, respectively

[80].

Lim et al. prepared mesoporous-structured graphene

powder through the method of thermal expansion

(Fig. 7) and used them as adsorbents for removing

VOCs. According to

Figure 8 the characteristics and

morphology of the prepared adsorbent was deﬁned

through different methods including scanning

electron microscopy (SEM), X-ray photoelectron

spectroscopy and N

isotherms. Adsorption

Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

Fig. 5. Toluene and acetaldehyde removal capacity by rGOMWKOH

compared to other adsorbents

[81].

Fig. 6. Interaction of amino graphene nanodots decorated functionalized graphene

sponge with formaldehyde molecules

capacity of graphene powder was examined using

propylene ﬁlter, at a concentration range of VOCs

(30, 50, 100 ppm). The results of the study indicated

that thermal expanded graphene powder (TEGP) is

an effective material for VOCs removal which acts

in a proper chemical oxidation using heat energy.

It was also reported that TEGP is of economical

materials, due to its reusability

[82].

3.2. Sole Gel Method

The sole-gel process is a method for producing solid

materials from small molecules. As a chemical-

wet technique, recently, it has been widely used

in the ﬁelds of material sciences and ceramic

engineering. This kind of methods are employed

Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al

Fig. 7. The scheme of thermal expansion mechanism; a: graphite powder b:

GO powder c: TEGP [82].

Fig. 8. SEM images of graphite powder (a,b), graphite oxide

(GO) (c,d) and TEGP (e,f) [82].

primarily for the synthesis of materials (mostly

metal oxides) starting with a chemical solution that

acts as a precursor for an integrated nexus of both

segregated particle and network polymer

[83].

Metal alkoxides and metal chlorides, which

are considered as frequent precursors, undergo

different forms of hydrolysis and poly-condensation

reactions. Binding of metal centers with either oxo

(M-O-M) or hydroxo (M-OH-M) bridges leads

to the formation of metal oxides and generates

metal-oxo or metal-hydroxo polymers in solution.

Therefore, the sol involves in the formation of a

gel-like diphasic system containing both solid

and liquid with segregated particles to a continues

polymer structure morphologies

[83].

The sole-gel method has been increasingly applied

for the development of various materials including

material for catalysis

[84, 85], chemical sensors

[86, 87], optical gain media [88], solid state

electrochemical devices

[88], photochromic and

non-linear applications

[90-92], membranes [93]

and ﬁbers

[94]. One of the intriguing applications

of the sole-gel technology is photo catalyst

preparation. Photo catalysts have been widely used

to degenerate VOCs. Common photo catalysts are

semiconductors like ZnO, GaP, TiO

, SiC, CdS and

[95]. Among these photo catalysts, TiO

the most applicable photo catalyst in the context

of eliminating environmental pollutants because of

its chemical stability, high oxidizing potential, low

cost, non-toxicity and environmentally friendly

properties

[96-99]. Parvizi et al. in their study about

perovskite nano-catalysts, synthesized a series of

La1-x Ax MnO

(A: Co, Zn, Mg, Ba) through sol-gel

method

(Fig. 9) and then evaluated the performance

of these catalysts in the elimination process of BTX

compounds. After conducting the research, the FTIR

results showed that all characteristics related to

efﬁcient catalyst was present in synthesized catalyst,

indicating acceptable outcomes of sol-gel method

[100]. By applying nonhydrolytic sol-gel method,

Debecker et al. synthesized V

-TiO

and added Mo

and W oxides to promote the catalysis performance

of catalyst

(Fig. 10). The results of the research

indicated a signiﬁcantly better oxidation performance

(93% oxidation) and a highly efﬁcient action for CO

selectivity for the purpose of VOCs removal

[101].

These results imply the importance of sol-gel method

in the process of efﬁcient catalyst synthesis.

Sarafraz Yazdi et al. developed a novel ﬁber

Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

Fig 9. Schematic procedure of La1-x Ax MnO3 (A: Co, Zn, Mg, Ba) perovskite nano-

catalyst preparation by sol-gel method [100].

to improve the elimination of trace amounts

of BTEX. At ﬁrst, poly ethylene glycol (PEG)

grafted on multi-walled carbon nanotubes (PEG-

g-MWCNTs) undergone a chemical bonding with

sol-gel to produce the unique ﬁber, as shown in

Figure 11. The results showed that the porous

structure, thermal stability, potent selectivity and

durability of mentioned ﬁber lead to a remarkably

better performance in the route of removing BTEX.

Also, due to porous structure of sol-gel coating, the

surface area of ﬁber, extraction velocity, steps of

desorption and capacity of sample loading increase

signiﬁcantly

[102].

3.3. Pervaporation

Membrane-based pervaporation (PV) technology

serves as an economical and alternative technique

in the organic-organic separation processes.

A number of researchers have reported the

elimination of VOCs from water sources which

has been achieved through various polymeric

membranes, using pervaporation technology

[103-

111]

. Uragami et.al prepared a PVC membrane

(hydrophobic polymeric membrane) and used

an ionic liquid (1-allyl-3-butylimidazolium bis

(triﬂuoromethane sulfonyl) imid (

[ABIM]TFIS))

with a remarkable and low afﬁnity for VOCs and

water, respectively. Through the process of PV,

Uragami and coworkers evaluated the performance

of prepared

[ABIM] [TFIS] /PVC aqueous

solutions of dilute benzene and reported that the

combination of PVC membranes with

[ABIM]

[TFIS]

ionic liquid represents higher permeability

and benzene/water selectivity in a concentration

dependent manner. As shown in

Figure 12, it

was also revealed that incorporation of PDMS

component decreases the density of membrane and

induces benzene permeability

[112]. Kujawa et al.

functionalized and increased the hydrophobicity of

two types of ceramic membranes with molecular

sizes of 5 kDa and 300 kDa

(Fig. 13). They reported

that membranes with increased hydrophobicity can

efﬁciently remove VOCs from binary aqueous

solutions through vacuum membrane distillation

procedure

[113].

Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al

Fig. 11. Sol-gel PEG-g-MWCNTs coating [102]

Fig. 10.

Nonhydrolytic sol-gel preparation method [101]

3.4. Catalytic oxidation

3.4.1.Regenerative catalytic oxidation (RCO)

In parallel with the regenerative thermal oxidation

(RTO), RCO is one of the most energy-saving

techniques, being as relatively similar working

mechanism as RTO. These techniques contain two

or more beds with random or structured ceramic

packs which are of high speciﬁc heat materials (800-

1000 J Kg

-1

) and perform as heat transfer media.

As shown in

Figure 14, frequently used two bed

RCO usually contains ceramic layer, catalyst layer,

natural gas burner or electrical heater which plays a

role as heat storage, reaction media and heat supply,

respectively. Due to its relatively lower price,

natural gas is preferred to use rather than electrical

heating. The mechanism of VOCs removal in this

technique involves passage of VOCs ﬂow from

ceramics cabinet A which preheats VOCs, followed

by a temperature increase up to 200-300

K. When

heater keeps the ﬂow temperature of catalyst (i.e.,

TChamber) higher than the light-off temperature

(TC), effective degradation of VOCs occurs.

Simultaneously, the releasing heat from VOCs

oxidation contributes to Tchamber and even can

Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

Fig. 12. The illustration of benzene permselectivity and benzene permeability

under the effect of PMMA—-PDMS membranes [112].

Fig. 13. Ceramic membrane’s functionalization by perﬂuoroalkylsilanes [113].

serve as a usable heat. In the next step, reacted ﬂow

goes down and its heat reserves as a high speciﬁc

heat, preheating the inlet VOCs ﬂow in the next

cabinet B to A cycle. Thermal Recovery Efﬁciency

() is a factor evaluating energy-efﬁciency related

properties of oxidizing equipment. Although the

 of RTO is up to 90%, the  of RCO

can reach 95% or higher

[114]. Liu et al.

designed a formula of Ru-5M/TiO

(M:

Mn, Co, Ce, Cu, Fe) for ruthenium-based

bimetallic catalyst and examined its effect

on benzene oxidation efﬁciency. After deep

examination of different bimetallic species,

it was proved that the combination of Ru-

5Co/ TiO

can be the most effective species

for the process of benzene removal.

Figure

Illustrates the represented mechanism of

benzene removal, using combined Ru-5Co/

TiO

catalyst [115]. In the study of Zhang

et al., nano-crystalline copper-manganese

oxides were prepared using sol-gel method.

The relativity between Cu and Mn was

deﬁned as Cu3x-Mnx (x can be equal to 0,

1, 1.5, 2, 2.5, 3 and is a representation of

molar ratio of Cu and Mn); the optimal ratio

was also found to be 2. Results showed that

CuMn

with the spinel structure of CuMn

exhibits a larger surface area, smaller pore

size and network oxygen species, leading to

enhanced catalytic activity of CuMn

which

can be the result of stabilized CuMn

active sites and synergistic effect between

Cu and Mn

(Fig. 16) [116].

3.4.2.Recuperative catalytic oxidation (CO)

Recuperative catalytic oxidation (CO),

known as a simpliﬁed version of RCO, is a

technique consisting of tubular or plate heat

exchanger instead of regenerative thermal

ceramic layers in RCO. In this technique,

at ﬁrst, a heat exchanger preheats VOCs

ﬂow, causing a temperature increase by

about 50-200

K. Then, the next heater

further heats the ﬂow up to the light-off

temperature of catalyst (usually above

573 K). Finally, reinforcement of VOCs oxidation

occurs to produce CO

and H

O with a signiﬁcant

amount of heat release. The  of a normal CO is

generally lower than 70%, indicating that the

costumer should cost more than usual to obtain

required energy for keeping the equipment to work

Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al

Fig. 14. The schematic diagram of regenerative catalytic oxidizer [114].

Fig. 15. Presented mechanism of the effect of Ru-5Co/ TiO

on the

benzene oxidation [115].

Fig. 16. The sample of CuMn

and relative spinel structure [116].

on VOCs elimination. In fact, CO can’t be effective

for large-scale and low concentrations of VOCs

pollutant removal

[117]. However, considering

low initial investment and high ﬂexibility, the

technique of CO can be effective for samples with

small ﬂowrate (<5000 m

-1

) of VOCs pollutant

[114]. Intriguingly, it is important to note that in

the case of large-volume and low concentration

VOCs emissions, there is an advanced technology

named adsorptive concentration-catalytic

oxidation which makes it possible to remove such

VOCs samples. Hoseini and coworkers aimed to

synthesize manganese oxide and impregnate it

into different loadings of alumina. They utilized

the resulted material in the procedure of BTX

oxidation followed by performance

analysis. Findings of the study represented

the most effective morphology and higher

surface area at 10% of alumina loading.

Further evaluation highlighted that the

best condition for oxidation is 10 kV, 0.2

g Mn10Al in the 200 mL min

-1

ﬂowrate of

pollutant with resulting oxidation of 97,

99 and 74% benzene, toluene and xylene,

respectively. The catalytic activity of catalyst

was investigated by catalyst calcination at

four different temperatures (400, 500, 600,

700

C). As Figure 17 it can be seen that the

highest level of BTX conversion was found

to be in Mn600 catalyst

[118]. Georgiev in

2019 investigated ozone-assisted catalytic

oxidation of benzene through alumina, silica

and boehmite-supported Ni/Pd catalysts in

353 K. Three bimetallic Ni/Pd samples in a

nano scale were synthesized with loadings

of 4.7% Ni, 0.17% Pd supported on SiO

AlOOH and Al

and by the means of

extractive-pyrolytic method. According to

the results of the study, the highest steady-

state activity of catalysts was attributed to

Ni/Pd/AlOOH catalyst

(Fig. 18). Georgiev

reported that this activity is dependent

on the amount of ozone decomposition

capacity of catalysts which leads to

oxidative species production; a sample

with a high ozone decomposition ability (related

to surface area of support) is capable of benzene

oxidation in a high extent

[119].

3.4.3.Photocatalytic oxidation (PCO)

As a different and distinguishable technology,

photocatalytic oxidation has received considerable

attention, due to its mild reaction condition and

non-selectivity. By using UV or visible light in the

environment temperature, photocatalytic oxidation

works different from thermal catalysis; therefore,

compared to RCO and CO, the conﬁguration of

PCO is simpler

(Fig. 19). Photocatalysis has a

wide variety of activities regarding various VOCs

at the environment temperature, however, due

Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

Fig. 17. The effect of manganese oxide calcination temperature on

the thermal oxidation of BTX [118].

Fig. 18. The XRD pattern of the Ni/Pd/AlOOH [119].

to low quantum efﬁciency and long residence

time requirement, it has a limited oxidizing

power and load adaptability

[114]. Zhang et al.

[120] introduced a new modiﬁed photocatalyst

named TiO

-UiO-66-NH

(constituting from

the combination of TiO

and UiO-66-NH

) and

reported that the new photocatalyst can signiﬁcantly

improve photocatalytic performance for VOCs

oxidation

(Fig. 20). According to this study, the

TiO

-UN photocatalytic system, represented good

selectivity and high photocatalytic activity

with 72.70 % of toluene decomposition during

240 min of reaction, which was even higher than

single TiO

(44.22 %) and UiO-66-NH

(7.48 %).

In the study of benzene removal by the means of

PCO technology, Ji J et al proposed that VUV-

PCO technique

(Fig. 21) is signiﬁcantly effective

in comparison with the ordinary UV-PCO

[121]. In

contrast to UV-PCO in which benzene degradation

is only attributed to photocatalytic oxidation, VUV-

PCO technique consists of several decomposition

pathways alongside VUV photolysis and PCO.

Benzene degradation hardly occurs under the effect

of UV irradiation

[122], however, VUV irradiation

have a benzene removal efﬁciency of about

48radiation potency in the process of benzene

degradation is related to the formation of hydroxyl

radicals (ŸOH) and oxygen species such as O(1D),

O(3P) and O

[123].

3.5. Ozonation-catalytic oxidation

Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al

Fig. 19. Schematic conﬁguration of PCO [114].

Fig. 20. Hypothesized pathways for photocatalytic oxidation of VOCs by TiO2-UiO-66-NH

[120].

In the technology of ozonation-catalytic oxidation,

Ozone (O

), a strong oxidant with a standard redox

potential at 2.07 eV, is used. Water sterilization and

wastewater treatment procedures have extensively

taken the advantages of ozone oxidation. Ozone

oxidation has been extensively applied

in water sterilization and wastewater

treatment procedures. Since ozone

isn’t very stable in gas environment,

as a single technique, it can’t be so

effective in the oxidation of VOCs

to CO

and H

O. However, ozone

oxidation has the capability of being

used as a pre-treatment step before

common catalytic techniques (e.g.

thermal catalysis and photocatalysis)

and promotes a synergistic effect

alongside these technologies. Rezaei

et al. in their 2013 study indicated

that transition metal oxide-based

catalysts propose efﬁcient VOCs

removal by catalytic ozonation,

obviating the need for costly noble

metals which are frequently used

in the VOCs catalytic combustion

with oxygen. The mentioned study

investigated different loadings of Mn

in a temperature range and reported

that increased temperature leads to

better activity of catalyst and lower

loadings of Mn resulting in surged and

efﬁcient toluene oxidation (analyzed

by GC-MASS) and ensuing ozone

decomposition (measured by ozone

analyzer)

(Fig. 22) [124]. Shu et al.

designed a novel process which was

a combination of VUV photolysis

and O

catalytic oxidation (VUV-

OZCO). In this system, VOCs are

ﬁrstly destructed by VUV and then are

oxidized through VUV-generated O

the presence of catalyst. O

by-product

is also eliminated simultaneously. In

the study of Shu et al. it was revealed

that the novel Mn-xCe-ZSM-5 catalyst

along with VUV-OZCO system

(Fig. 23) can have

the capacity to simultaneously decompose O

by-

product and improve toluene removal efﬁciency

[125].

3.6. Non-thermal plasma-catalytic oxidation

Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

Fig. 21.

The schematic diagram of VUV-PCO system [121].

Fig. 22. The scheam of experimental procedure [126].

Fig. 23. VUV-OZCO process [125].

Non-thermal plasma (NTP) which has

been introduced as green technology

for elimination of VOCs from indoor

and industrial gas streams, is a

superior source of chemically active

species (OH and O

radicals, ions,

excited species, etc). This property

leads non-thermal plasma to provide

a highly reactive environment

(caused by electron’s acceleration,

dissociation and ionization); without

any energy consumption on heating

the entire gas stream, in which

reactive species oxidize various VOCs

molecules and consequently degrade

them. Besides low energy efﬁciency

and inferior CO

selectivity, a major

difﬁculty with non-thermal plasma is

production of by-products including

NOX, O

and other intermediates

relating to the fact that electrons do

not have enough energy to mineralize

BTX molecules

[127]. Thus, non-

thermal plasma oxidation can’t be

considered as a single technique to

deal with VOCs pollution, because

products of uncompleted reactions in

this technique can act as secondary

pollutions on their own.

A great solution for the aforementioned

problem is combining the non-thermal

plasma oxidation with catalysis

(Fig.

24)

. This combination has been

extensively investigated during the

last decade, indicating that the system

of non-thermal plasma-catalysis

is obviously capable of improving

energy efﬁciency and suppressing

unwanted by-products in the process

of VOCs degradation

[128]. Non-

thermal plasma catalysis system consists of

two conﬁgurations: in-plasma catalysis (IPC)

and post-plasma catalysis (PPC). Guo et al.

investigated the efﬁciency of NTP+ MnOx

catalyst in the elimination of benzene and showed

that this combination can signiﬁcantly improve

benzene removal efﬁciency and promote CO

formation, with a simultaneously suppression of

[129].

In the study of Jiang et al. both IPC and PPC

Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al

Fig. 24. Experimental setup of hybrid plasma-catalytic system for

oxidation of VOCs [115].

Fig. 25. Different plasma-catalysis systems in IPC and PPC

conﬁgurations: (a) catalysts in the region I, (b) catalysts in the

downstream of region I, (c) catalysts in the region II, (d) catalysts in

the downstream of region II [130].

conﬁgurations of NTP

(Fig. 25) constituted from

a hybrid surface/packed bed discharge (HSPBD)

with different catalysts including Agx Ce1-x/-

was applied. From the result of the study,

it was revealed that through the plasma-catalysis

system and present of Agx Ce1-x/-Al

catalyst

signiﬁcantly enhance benzene degradation and

improve COx selectivity. The study of Jiang also

showed that the PPC process has a better effect

on the decomposition of O

and benzene [130].

3.7. Nanotechnology

Nanotechnology is an increasingly important area

of the recent technology, playing a cardinal role

in a bunch of ﬁelds. Among the various subtypes

of this technology, carbon nanotubes (CNTs) has

attracted a great deal of interest in the context of

industrial applications and implementations. As

shown in

Figure 26 and based on the number of

the structure layers, CNTs are classiﬁed as single

walled carbon nanotubes (SWCNTs) and multi

walled carbon nanotubes (MWCNTs).

Pourfayaz et al. evaluated the adsorption capacity

of two types of multi walled carbon nanotubes

(MWCNTs)

(Fig. 27) with different functional

groups and analyzed them using gas chromatography

(GC). Conﬁrmation of functionalization was

performed through fourier transform infrared

(FTIR). The observed ﬁndings demonstrated that

the MWCNTs with a larger surface area and higher

crystallinity have a signiﬁcant adsorption capacity

for both benzene and toluene

[132].

4. Comparing of diriment sorbent for

removal VOCs from waters/gas

The removal procedure for VOCs from waters

was compared by different analyzer such as GC-

MS,GC-FID, HS-GC-MS, GC-FID/ HPLC-UV,

SWV and HPLC which was shown in

Table 1.

Due to

Table 1, the different sorbents and techniques

compared as detection limit (LOD), recovery( R),

relative standard deviation(RSD%), adsorption/

desorption, temperature(T) and absorption

capacity(AC) in water samples.

Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

Fig. 26. The conceptual scheme representing general

dimensions of the length and width of single walled

carbon nanotubes (SWCNTs) and multi walled carbon

nanotubes (MWCNTs) [131].

Fig. 27. Schematic diagram of experiment setup

toward measurement of adsorption capacity of

MWCNTs [132].

Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al

VOCs Method An alyzer Analytical Features Matrix Ref.

BTEX ASTM GC-MS LOD: 0.11–0.48

Recovery: 94–107%

Water [133]

BTEX DAI GC-FID LOD: 0.61–1.11

Recovery: 95-99%

Water [134]

BTEX Sorbent HS-GC-MS LOD: 0.001–0.05

RSD: <4.2%

Water [135]

BTX LV-LLE GC-FID

HPLC-UV

RSD: 2.4-11.9

R: 0.8452-0.9999

Permenkes:0.01-0.7

Deviation: 2.13-10.96

LOD:0.1-0.3

Water [136]

BTEX CBD-DE SWV LOD B:3.0×10

7

molL

1

LODT:8.0×10

7

molL

1

LOD X: 9.1×10

7

 molL

1

Recovery: 98.9-99.4

Water [137]

ROS SE-UOOG GC LOD: 0.023 mg/g

RSD: <2%

Recovery: 95.4-102%

Water

[138]

p-xylene SLS-MOF/ zeolites SOM Recovery: more than 95%

Selectivity values of 24.0, 10.4 and

6.2 vs. oX, eB and mX

Water /

Gas

[139]

Benzene D – -SPE SHS-GC-MS

AC: CNTs@PhSA,157.34 mg g

-1

AC: CNTs, 157.34 mg g

-1

Recovery: 96.8-102

Water

[140]

Toluene G-PhAPTMS,

- SGEP GC-FID

GC-MS

Removal efﬁciency:> 95%

Adsorption: Chemical and physical

Flow rate : 200 ml min

-1

Temperature: 40

Air [140]

benzene

toluene

copper oxide

nanoparticles (CuO-

NPs)

HS-GC AC for benzene: 100.24mg g

-1

AC for toluene: 111.31 mg g

-1

Adsorption efﬁciency : 98.7% for

benzene

Adsorption efﬁciency : 92.5% for

toluene

Water [142]

VOCs SPME-sol-gel

SWCNT / silica

GC-MS LOD: 0.09–0.2 ng mL

-1

Adsorption: 15 min for 25

Desorption: 3 min for 280

air [143]

Formaldehyde SPME PDMS-DVB GC-MS LOD: 0.002–0.032 g m

-3

Adsorption: 15 min for 25

Desorption: 4 min for 250

Air

water

[144]

phenol HS-SPME CW-DVB GC-MS LOD: 1.13–4.60 ngmL

-1

water [145]

Alkyl PAH HS-SPME- PDMS GC-MS LOD: 0.002–0.6 ng mL

1

water [146]

Volatile sulfur HS-SPME-PDMS-

CAR

GC-FPD LOD: 1.6–93.5 ng L

1

water

lakes

[147]

PBDE DI-SPME MWCNT GCECD LOD: 3.6–8.6 ng L

1

Recovery: 90–119%

river

water

[148]

OCP HS-SPME GCECD LOD: 0.16–0.84 ng L

1

Recovery: 63–127%

Sea

water

[149]

VOCs 3D-SPE-CB-PLA) HPLC r

=0.96

Inﬁll print densities: 15 - 50%.

Ambient temperatures : 19.0±0.5 °C

water [150]

Table1. Determination and separation VOCs from water/gas by different sorbents and methods

AC: Absorption Capacity

GC-MS: Gas chromatography mass spectrometry

GC-FID: Gas chromatography equipped with ﬂame

ionization detector

SWV: Square wave voltammetry

SHS-GC-MS: Head space gas chromatography mass

spectrometry

GC: Gas Chromatography

SOM: Sized Organic Molecules

ROS: Residual organic solvent (

ethanol,

tetrahydrofuran, cyclohexane, n-heptane

)

D- -SPE: Dispersive micro solid phase extraction

method

SLS: Solid liquid separation

SE-UOOG: Solvent extraction-Unconventional oil

ore Gangues

CBD-DE: Cathodically pretreated boron doped

diamond electrode

LV-LLE: Low volume liquid-liquid extraction

DAI: Direct aqueous injection

ASTM: ASTM D-5790 Purge and trap

G-PhAPTMS

- SGEP: Functionalizing graphene with

N-Phenyl-3-aminopropyl trimethoxy

-sorbent gas

extraction

HS-GC: Headspace gas chromatograph

3D-SPE-CB-PLA: 3D printed solid-phase extraction

carbon black modiﬁed polylactic acid (PLA)

OCP: Organo chlorine pesticides

PBDE: Polybrominated diphenyl ethers ACN:

acetonitrile

BTEX: benzene, toluene, ethyl benzene, ortho-xylene

and meta- and para-xylene

BTX: benzene, toluene and xylene

DAD: diode array detector

DI: direct immersion

ECD: electron capture detector

FID: ﬂame ionization detector

FPD: ﬂame photometric detector

FD: ﬂuorescence detection

LOD: limit of detection (g L

1

)

LOQ: limit of quantiﬁcation (g L

1

)

MA: microwave assisted

MAE: microwave assisted extraction

MW: multiwalled; PAHs: polycyclic aromatic

hydrocarbons

PDMSAC: PDMS mixed with activated C

TSD: thermoionic speciﬁc detection

5. Conclusions

Through entering from different sources such

as water, air and foods, the VOCs cause several

diseases in humans. So, the environmental

samples such as water, wastewater and air

must be controlled and determined by applied

methodologies. The human life depends on

water future and elimination of pollutions such

as VOCs in waters. By growing economy and

increasing population, the main theme is water

supplies without any contaminations. Quantity and

quality of water must be checked daily and main

parameters of waters should be controlled. So,

the water, especially drinking water conservation

is extremely important, and contaminations such

as BTEX, VOCs and other organic pollutions in

waters should be removed by new technologies.

The technologies based on sorbents depend on

water characteristics, affordability, acceptability

and level of application. Every methodology for

VOCs removal from waters have many advantages

and disadvantages for water treatment. Therefore,

the important parameters for any methodology

such as speed, simplicity and selectivity must be

studied. The vary methodology such as, solid phase

extraction, liquid phase extraction, the adsorption/

desorption, the sole gel technology, RCO, CO

and PCO have been used for VOCs removal from

waters. In this review the recent technologies based

on sorbents or catalysts are introduced for VOCs

removal from water samples.

6. Acknowledgement

This review was supported by the Science and

Research Branch, Islamic Azad University and

Dr. Hamid Shirkhanloo in Research Institute of

Petroleum Industry of Iran.

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