Anal. Method Environ. Chem. J.

3 (2) (2020) 34-58

Research Article, Issue 2

Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir

AMECJ

A Review, Methods for removal and adsorption of volatile

organic compounds from environmental matrixes
Shahnaz Teimooria, Amir Hessam Hassanib,* Mostafa Panahic and Nabiollah Mansourid
a
PhD student of environmental engineering, Faculty of Natural Resources and Environment,
Science and Research Branch, Islamic Azad University, Tehran, Iran
b
Department of environmental engineering, Faculty of Natural Resources and Environment,
Science and Research Branch, Islamic Azad University, Tehran, Iran
C
Department of environmental engineering, Faculty of Natural Resources and Environment,
Science and Research Branch, Islamic Azad University, Tehran, Iran
d
Department of environmental engineering, Faculty of Natural Resources and Environment,
Science and Research Branch, Islamic Azad University, Tehran, Iran

ARTICLE INFO: ABSTRACT

Received 6 Mar 2020 The volatile organic compounds (VOCs) have toxic effects on human
health and environmental matrices. So, determination and removal of
Revised form 5 May 2020 VOCs from the environmental samples such as water, wastewater and air
Accepted 30 May 2020 are very important as they exert toxic effects on human. Many chemical
Available online 30 Jun 2020 techniques such as; analytical methods for sorbents (extraction, adsorption),
------------------------ sole gel method, pervaporation, regenerative catalytic oxidation (RCO),
recuperative catalytic oxidation (CO), adsorptive concentration-catalytic
Keywords: oxidation, photocatalytic oxidation (PCO), ozonation-catalytic oxidation
Volatile organic compounds, and non-thermal plasma-catalytic oxidation, have been used for removal
Chemistry and biochemistry method, and reduction of VOCs from different matrices. This review study has
Removal, been conducted to collect the adsorbents and applied chemistry methods
Adsorption, which have been recently used in different works for the elimination of
Water and air VOCs from air and water samples.

1. Introduction as the most hazardous materials in the volatile

Volatile organic compounds (VOCs) enter the organic compounds family and regarding their
environment through various sources, leaving importance, a considerable amount of literature
severe environmental and health impacts [1]. has been published on the issue of benzene and
The production of industrial wastewater is the toluene potential adverse effects on health [13-
main origin of VOCs which is considered as a 16]. According to the international agency for
negative aspect of industrial activity, exerting research on cancer [17], benzene is categorized as
several adverse effects on the environment and group 1 (carcinogenic to humans) and Toluene as
human health [2-6]. Volatile organic compounds group 2B (quietly carcinogenic to humans). What
are one of the most widely used materials we know about the adverse effects of benzene and
in the production of refrigerants, plastics, Toluene is largely based on previous studies which
adhesives, paints, and petroleum products [3, have proved that the common adverse effects
5, 7-12]. Benzene and toluene are regarded of these organic compounds is neurotoxicity
including drowsiness, headache, tremor, coma and
*
Corresponding Author: Amir Hessam Hassani dizziness [16, 18-20]. Benzene exposure has been
Email: [email protected] reported to increase the risk of various cancers
https://doi.org/10.24200/amecj.v3.i02.100 including leukemia and hematopoietic cancers
 Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al 35

[15, 21]. It has been also recognized that benzene the process of VOCs elimination.
and Toluene affect skin, eyes and respiratory
tract by inducing irritation [22-25]. Increased 2. Data sources
threatening impacts of VOCs increase health In this review, we used information such as
and environment concern and therefore, there is journal articles, statistical data and conferences/
a crucial need to develop effective strategies to seminars papers as our data source. Surfing
remove them. Several attempts have been made in scientific websites and databases including
to eliminate or recover VOCs from wastewater; Google Scholar and Web of Science was a major
for example, distillation is commonly used, way of accessing valuable information and related
regardless of azeotropes formation or high energy articles. Therefore, it was important to search at
consumption [6, 7, 10, 12, 26-29]. Hitherto, a least one of related key words which are included
number of approaches including adsorption [30- in either titles or abstracts of papers and are as
32], condensation [33], incineration [34, 35] and follows: “VOCs removal”, “Catalytic oxidation”,
thermal oxidation [36] have been established “Adsorbents” and “Nanomaterials”. It was also
to eliminate VOCs from the environment. crucial for papers to contain one or more of the
Treatment methods that have been established aforementioned keywords to be embodied in this
for VOCs removal are as follows: air stripping, review.
adsorption, advance oxidation, distillation,
anaerobic/aerobic biological treatment and the 3. Experimental procedures and methods
technology of membrane [27, 29, 37-42]. Many 3.1. Sorbent Methods
researchers have also applied pervaporation with The analytical methods for sorbents based on
nonporous membranes such as silicon rubber- extraction and adsorption (chemical and physical)
coated PP to remove aromatic compounds from were used for VOCs removal from water and
water sources [43-45]. Moreover, a large body wastewater samples. Recently, the phenyl
of studies has taken the advantage of membrane- sulfonic acid (PhSA) modified carbon nanotubes
based air stripping (MAS) process by the means (CNTs) were presented for benzene removal
of microporous hollow fiber contactors which (BR) from waters. For separation process, the
is very effective in the treatment of aqueous PhSA@CNTs based on the dispersive micro solid
effluents containing VOCs [46-56]. In the context phase extraction method (D- μSPE) was used
of catalytic oxidation (one of the used techniques for BR from water. The main mechanism was
for VOCs removal), many researchers have achieved by the polar–π or π–π electron donor–
focused on catalysts including noble metals (e.g. acceptor interactions between the benzene and
Al2O3, TiO2, CeO2, MnOx), nonmetal oxides (e.g. SO3H /C6H5 group of CNTs surface (Fig. 1).
SiO2), zeolites (e.g. ZSM, MCM, NaY) [57-62] According to the procedure, 10 mg of CNTs@
and carbon derivatives [63, 64]. However, metal PhSA nanostructures was added to 5 mL of water
oxides that are in charge of VOCs elimination samples with different benzene standard solution
are mostly derivatives of elements distributed in (0.1--10 mg L-1) in GC vial. After shacking
groups III-B through II-B of the periodic table and centrifuging (3500rpm), the CNTs@PhSA
such as Ti, Cu, Mn, Al, Ce, Co, Fe and so on [65- sorbent separated from water samples and finally,
67]. Despite extensive attempts toward VOCs its concentration was determined by static head
removal, conducted technologies have, to some space gas chromatography mass spectrometry
extent, shortcomings and limitations. This paper (SHS-GC-MS) [68]. The mechanism based on
aims to review techniques used for VOCs removal CNTs@PhSO3H was obtained with π–π stacking
and discuss their advantages/disadvantages and between aromatic chain and S=O bond of
finally, focus on introduced solutions to improve CNTs@PhSO3H (Fig. 2).
36 Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

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

method

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

The graphene based materials (GBMs) have been also of the GO structures are shown in Figure 3 which
used as a new technology in different fields of science was used for VOCs removal in different matrices.
specially in the environmental chemistry. The GBMs Hofmann and Holst first introduced graphite oxide
adsorbent was used for the removal of VOCs with and then Ruess et al designed a graphite oxide
high adsorption capacity and cost-effectivity through structure based on a wrinkled carbon sheet. Scholz
various functionalization processes on the surface. and Boehm showed that the carbon sheet replaced by
The intermolecular forces of GBMs with the gaseous carbonyl and hydroxyl. Nakajima and Matsuo used
pollutants caused gas adsorption. The strength of the two carbon layers linked to each other by sp3 CeC
interaction of GBMs with VOCs depended on surface bonds with carbonyl and hydroxyl groups. Lerf et al
area/properties, pore volume/size of the GBMs. suggested a graphite oxide based on the unoxidized
The GBMs showed the excellent adsorption for the rings of benzene and that a wrinkled region of alicyclic
removal of VOCs. Among the different graphene 6- membered ring ethers is distributed randomly in a
structures, GO and rGO have mostly used for the flat aromatic region. Szabó et al., showed a carbon
VOC removal from waters [69]. The various models network structure [70-73].
 Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al 37

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

benzene, toluene, and xylene (BTX) are the small molecules under ambient conditions. So,
major members of VOCs pollutions. These the GO/MOF-5 composite was prepared using
VOCs are preferably adsorbed on hydrophobic varying proportions of GO, such as 1.75 wt%,
surfaces as compared to hydrophilic surfaces 3.5 wt%, 5.25 wt%, and 7 wt% (Fig 4).
[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 (π-π bonds), increasing
the adsorption capacity of VOCs relative to GO
sorbents. In addition, the surface areas for rGO
and GO were achieved 292.6 m2 g-1 and 236.4
m2 g-1, respectively and due to high surface
area of rGO, the adsorption capacity of VOCs
Fig. 4. Adsorption-desorption isotherms for graphene
was increased [69, 74, 75]. Szczęśniak et al
oxide/metal organic framework-5 (GO/MOF-5)
showed that the high surface area of GBMs and
for benzene [78]. MG (1–4) represents GO/MOF-5
GO caused to improve the benzene adsorption
composite with 1.75%, 3.5%, 5.25%, and 7% of GO
capacities for OMC. The incorporation of
in MOF-5.
GO with OMC / KOH increased the surface
area from 740 m2 g-1 to 1370 m2 g-1. Also, the
The GO and rGO was used for the removal of
pore volume of OMC from 0.61 increased to
toluene by Kim et al. The π–π bonds, hydrophobic
1.06 cm3 g-1 after the formation of GO/OMC.
and electrostatic interaction with toluene led to
Finally, adsorption capacities for benzene were
the absorption of toluene on GO / rGO surfaces
obtained 633 mg g-1 and 750 mg g-1 for OMC
(Fig. 5). Different types of GBMs such as graphene
and GO/OMC, respectively [76-77]. GO - MOF-
platelets (GP), rGOMW, and KOH activated
5 was used for the removal of benzene vapor
rGOMW (rGOMWKOH)) were analyzed for the
from air with capacity of 251 mg g-1 [78]. Due
toluene adsorption [79].
to high porosity of MOFs, they cannot retain
38 Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

Fig. 5. Toluene and acetaldehyde removal capacity by rGOMWKOH

compared to other adsorbents [81].
Aldehyde and ketone compounds are the most the adsorption capacity of GGND/S and G/S
carbonyl VOCs which can be considered as were achieved 22.8 mg/g-1 and 7.5 mg/g-1 for
sources of the environment contamination. GBMs formaldehyde, respectively [80].
can efficiently remove the carbonyl compounds Lim et al. prepared mesoporous-structured graphene
from environment. For indoor formaldehyde powder through the method of thermal expansion
removal, amino functionalized graphene sponge (Fig. 7) and used them as adsorbents for removing
(G/S) or G/S decorated with graphene nanodots VOCs. According to Figure 8 the characteristics and
(G-GND/S) were used by Wu et al. G-GND/S morphology of the prepared adsorbent was defined
with high amine groups on surface as compared to through different methods including scanning
G/S caused a high interaction with formaldehyde electron microscopy (SEM), X-ray photoelectron
molecules (Fig 6). The results showed that spectroscopy and N2 isotherms. Adsorption

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

sponge with formaldehyde molecules
 Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al 39

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].
capacity of graphene powder was examined using materials, due to its reusability [82].
propylene filter, at a concentration range of VOCs 3.2. Sole Gel Method
(30, 50, 100 ppm). The results of the study indicated The sole-gel process is a method for producing solid
that thermal expanded graphene powder (TEGP) is materials from small molecules. As a chemical-
an effective material for VOCs removal which acts wet technique, recently, it has been widely used
in a proper chemical oxidation using heat energy. in the fields of material sciences and ceramic
It was also reported that TEGP is of economical engineering. This kind of methods are employed
40 Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

primarily for the synthesis of materials (mostly semiconductors like ZnO, GaP, TiO2, SiC, CdS and
metal oxides) starting with a chemical solution that Fe2O3 [95]. Among these photo catalysts, TiO2 is
acts as a precursor for an integrated nexus of both the most applicable photo catalyst in the context
segregated particle and network polymer [83]. of eliminating environmental pollutants because of
Metal alkoxides and metal chlorides, which its chemical stability, high oxidizing potential, low
are considered as frequent precursors, undergo cost, non-toxicity and environmentally friendly
different forms of hydrolysis and poly-condensation properties [96-99]. Parvizi et al. in their study about
reactions. Binding of metal centers with either oxo perovskite nano-catalysts, synthesized a series of
(M-O-M) or hydroxo (M-OH-M) bridges leads La1-x Ax MnO3 (A: Co, Zn, Mg, Ba) through sol-gel
to the formation of metal oxides and generates method (Fig. 9) and then evaluated the performance
metal-oxo or metal-hydroxo polymers in solution. of these catalysts in the elimination process of BTX
Therefore, the sol involves in the formation of a compounds. After conducting the research, the FTIR
gel-like diphasic system containing both solid results showed that all characteristics related to
and liquid with segregated particles to a continues efficient catalyst was present in synthesized catalyst,
polymer structure morphologies [83]. indicating acceptable outcomes of sol-gel method
The sole-gel method has been increasingly applied [100]. By applying nonhydrolytic sol-gel method,
for the development of various materials including Debecker et al. synthesized V2O5-TiO2 and added Mo
material for catalysis [84, 85], chemical sensors and W oxides to promote the catalysis performance
[86, 87], optical gain media [88], solid state of catalyst (Fig. 10). The results of the research
electrochemical devices [88], photochromic and indicated a significantly better oxidation performance
non-linear applications [90-92], membranes [93] (93% oxidation) and a highly efficient action for CO2
and fibers [94]. One of the intriguing applications selectivity for the purpose of VOCs removal [101].
of the sole-gel technology is photo catalyst These results imply the importance of sol-gel method
preparation. Photo catalysts have been widely used in the process of efficient catalyst synthesis.
to degenerate VOCs. Common photo catalysts are Sarafraz Yazdi et al. developed a novel fiber

Fig 9. Schematic procedure of La1-x Ax MnO3 (A: Co, Zn, Mg, Ba) perovskite nano-
catalyst preparation by sol-gel method [100].
 Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al 41

to improve the elimination of trace amounts 3.3. Pervaporation

of BTEX. At first, poly ethylene glycol (PEG) Membrane-based pervaporation (PV) technology
grafted on multi-walled carbon nanotubes (PEG- serves as an economical and alternative technique
g-MWCNTs) undergone a chemical bonding with in the organic-organic separation processes.
sol-gel to produce the unique fiber, as shown in A number of researchers have reported the
Figure 11. The results showed that the porous elimination of VOCs from water sources which
structure, thermal stability, potent selectivity and has been achieved through various polymeric
durability of mentioned fiber lead to a remarkably membranes, using pervaporation technology [103-
better performance in the route of removing BTEX. 111]. Uragami et.al prepared a PVC membrane
Also, due to porous structure of sol-gel coating, the (hydrophobic polymeric membrane) and used
surface area of fiber, extraction velocity, steps of an ionic liquid (1-allyl-3-butylimidazolium bis
desorption and capacity of sample loading increase (trifluoromethane sulfonyl) imid ([ABIM]TFIS))
significantly [102]. 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].
Fig. 10. Nonhydrolytic sol-gel preparation method [101]

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

42 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].

3.4. Catalytic oxidation role as heat storage, reaction media and heat supply,
3.4.1.Regenerative catalytic oxidation (RCO) respectively. Due to its relatively lower price,
In parallel with the regenerative thermal oxidation natural gas is preferred to use rather than electrical
(RTO), RCO is one of the most energy-saving heating. The mechanism of VOCs removal in this
techniques, being as relatively similar working technique involves passage of VOCs flow from
mechanism as RTO. These techniques contain two ceramics cabinet A which preheats VOCs, followed
or more beds with random or structured ceramic by a temperature increase up to 200-300 OK. When
packs which are of high specific heat materials (800- heater keeps the flow temperature of catalyst (i.e.,
1000 J Kg-1 K-1) and perform as heat transfer media. TChamber) higher than the light-off temperature
As shown in Figure 14, frequently used two bed (TC), effective degradation of VOCs occurs.
RCO usually contains ceramic layer, catalyst layer, Simultaneously, the releasing heat from VOCs
natural gas burner or electrical heater which plays a oxidation contributes to Tchamber and even can
 Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al 43

serve as a usable heat. In the next step, reacted flow 573 K). Finally, reinforcement of VOCs oxidation
goes down and its heat reserves as a high specific occurs to produce CO2 and H2O with a significant
heat, preheating the inlet VOCs flow in the next amount of heat release. The η of a normal CO is
cabinet B to A cycle. Thermal Recovery Efficiency generally lower than 70%, indicating that the
(η) is a factor evaluating energy-efficiency related costumer should cost more than usual to obtain
properties of oxidizing equipment. Although the required energy for keeping the equipment to work
η of RTO is up to 90%, the η of RCO
can reach 95% or higher [114]. Liu et al.
designed a formula of Ru-5M/TiO2 (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/ TiO2 can be the most effective species
for the process of benzene removal. Figure
15 Illustrates the represented mechanism of
benzene removal, using combined Ru-5Co/
TiO2 catalyst [115]. In the study of Zhang Fig. 14. The schematic diagram of regenerative catalytic oxidizer [114].
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
CuMn2 with the spinel structure of CuMn2O4
exhibits a larger surface area, smaller pore
size and network oxygen species, leading to
enhanced catalytic activity of CuMn2 which
can be the result of stabilized CuMn2O4
active sites and synergistic effect between
Cu and Mn (Fig. 16) [116].
Fig. 15. Presented mechanism of the effect of Ru-5Co/ TiO2 on the
3.4.2.Recuperative catalytic oxidation (CO) benzene oxidation [115].
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 50-200OK. Then, the next heater
further heats the flow up to the light-off
temperature of catalyst (usually above Fig. 16. The sample of CuMn2 and relative spinel structure [116].
44 Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

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 oC). As Figure 17 it can be seen that the
Fig. 17. The effect of manganese oxide calcination temperature on highest level of BTX conversion was found
the thermal oxidation of BTX [118]. 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 SiO2,
AlOOH and Al2O3 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
Fig. 18. The XRD pattern of the Ni/Pd/AlOOH [119].
capacity of catalysts which leads to
oxidative species production; a sample
on VOCs elimination. In fact, CO can’t be effective with a high ozone decomposition ability (related
for large-scale and low concentrations of VOCs to surface area of support) is capable of benzene
pollutant removal [117]. However, considering oxidation in a high extent [119].
low initial investment and high flexibility, the
technique of CO can be effective for samples with 3.4.3.Photocatalytic oxidation (PCO)
small flowrate (<5000 m h ) of VOCs pollutant
3 -1
As a different and distinguishable technology,
[114]. Intriguingly, it is important to note that in photocatalytic oxidation has received considerable
the case of large-volume and low concentration attention, due to its mild reaction condition and
VOCs emissions, there is an advanced technology non-selectivity. By using UV or visible light in the
named adsorptive concentration-catalytic environment temperature, photocatalytic oxidation
oxidation which makes it possible to remove such works different from thermal catalysis; therefore,
VOCs samples. Hoseini and coworkers aimed to compared to RCO and CO, the configuration of
synthesize manganese oxide and impregnate it PCO is simpler (Fig. 19). Photocatalysis has a
into different loadings of alumina. They utilized wide variety of activities regarding various VOCs
the resulted material in the procedure of BTX at the environment temperature, however, due
 Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al 45

to low quantum efficiency and long residence PCO technology, Ji J et al proposed that VUV-
time requirement, it has a limited oxidizing PCO technique (Fig. 21) is significantly effective
power and load adaptability [114]. Zhang et al. in comparison with the ordinary UV-PCO [121]. In
[120] introduced a new modified photocatalyst contrast to UV-PCO in which benzene degradation
named TiO2-UiO-66-NH2 (constituting from is only attributed to photocatalytic oxidation, VUV-
the combination of TiO2 and UiO-66-NH2) and PCO technique consists of several decomposition
reported that the new photocatalyst can significantly pathways alongside VUV photolysis and PCO.
improve photocatalytic performance for VOCs Benzene degradation hardly occurs under the effect
oxidation (Fig. 20). According to this study, the of UV irradiation [122], however, VUV irradiation
TiO2-UN photocatalytic system, represented good have a benzene removal efficiency of about
CO2 selectivity and high photocatalytic activity 48radiation potency in the process of benzene
with 72.70 % of toluene decomposition during degradation is related to the formation of hydroxyl
240 min of reaction, which was even higher than radicals (ŸOH) and oxygen species such as O(1D),
single TiO2 (44.22 %) and UiO-66-NH2 (7.48 %). O(3P) and O3 [123].
In the study of benzene removal by the means of 3.5. Ozonation-catalytic oxidation

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

Fig. 20. Hypothesized pathways for photocatalytic oxidation of VOCs by TiO2-UiO-66-NH2 [120].
46 Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

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 CO2 and H2O. However, ozone
oxidation has the capability of being
used as a pre-treatment step before
Fig. 21. The schematic diagram of VUV-PCO system [121]. 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
Fig. 22. The scheam of experimental procedure [126].
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 O3 catalytic oxidation (VUV-
OZCO). In this system, VOCs are
firstly destructed by VUV and then are
oxidized through VUV-generated O3 in
the presence of catalyst. O3 by-product
is also eliminated simultaneously. In
Fig. 23. VUV-OZCO process [125]. the study of Shu et al. it was revealed
that the novel Mn-xCe-ZSM-5 catalyst
In the technology of ozonation-catalytic oxidation, along with VUV-OZCO system (Fig. 23) can have
Ozone (O3), a strong oxidant with a standard redox the capacity to simultaneously decompose O3 by-
potential at 2.07 eV, is used. Water sterilization and product and improve toluene removal efficiency
wastewater treatment procedures have extensively [125].
taken the advantages of ozone oxidation. Ozone 3.6. Non-thermal plasma-catalytic oxidation
 Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al 47

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 O2- 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 Fig. 24. Experimental setup of hybrid plasma-catalytic system for
the entire gas stream, in which oxidation of VOCs [115].
reactive species oxidize various VOCs
molecules and consequently degrade
them. Besides low energy efficiency
and inferior CO2 selectivity, a major
difficulty with non-thermal plasma is
production of by-products including
NOX, O3 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 Fig. 25. Different plasma-catalysis systems in IPC and PPC
is obviously capable of improving configurations: (a) catalysts in the region I, (b) catalysts in the
energy efficiency and suppressing downstream of region I, (c) catalysts in the region II, (d) catalysts in
unwanted by-products in the process the downstream of region II [130].
of VOCs degradation [128]. Non-
thermal plasma catalysis system consists of that this combination can significantly improve
two configurations: in-plasma catalysis (IPC) benzene removal efficiency and promote CO2
and post-plasma catalysis (PPC). Guo et al. formation, with a simultaneously suppression of
investigated the efficiency of NTP+ MnOx CO [129].
catalyst in the elimination of benzene and showed In the study of Jiang et al. both IPC and PPC
48 Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

configurations of NTP (Fig. 25) constituted from (MWCNTs) (Fig. 27) with different functional
a hybrid surface/packed bed discharge (HSPBD) groups and analyzed them using gas chromatography
with different catalysts including Agx Ce1-x/ɣ- (GC). Confirmation of functionalization was
Al2O3 was applied. From the result of the study, performed through fourier transform infrared
it was revealed that through the plasma-catalysis (FTIR). The observed findings demonstrated that
system and present of Agx Ce1-x/ɣ-Al2O3 catalyst the MWCNTs with a larger surface area and higher
significantly enhance benzene degradation and crystallinity have a significant adsorption capacity
improve COx selectivity. The study of Jiang also for both benzene and toluene [132].
showed that the PPC process has a better effect
on the decomposition of O3 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

Fig. 27. Schematic diagram of experiment setup

toward measurement of adsorption capacity of
MWCNTs [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.
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].
 Removal and adsorption of volatile organic compounds Shahnaz Teimoori et al 49

Table1. Determination and separation VOCs from water/gas by different sorbents and methods
VOCs Method Analyzer Analytical Features Matrix Ref.
BTEX ASTM GC-MS LOD: 0.11–0.48 Water [133]
Recovery: 94–107%
BTEX DAI GC-FID LOD: 0.61–1.11 Water [134]
Recovery: 95-99%
BTEX Sorbent HS-GC-MS LOD: 0.001–0.05 Water [135]
RSD: <4.2%
BTX LV-LLE GC-FID RSD: 2.4-11.9 Water [136]
HPLC-UV R: 0.8452-0.9999
Permenkes:0.01-0.7
Deviation: 2.13-10.96
LOD:0.1-0.3
BTEX CBD-DE SWV LOD B:3.0×10−7 mol L−1 Water [137]
LODT:8.0×10−7 mol L−1
LOD X: 9.1×10−7  mol L−1
Recovery: 98.9-99.4
ROS SE-UOOG GC LOD: 0.023 mg/g Water [138]
RSD: <2%
Recovery: 95.4-102%
p-xylene SLS-MOF/ zeolites SOM Recovery: more than 95% Water / [139]
Selectivity values of 24.0, 10.4 and Gas
6.2 vs. oX, eB and mX
AC: CNTs@PhSA,157.34 mg g-1 Water
Benzene D – μ-SPE SHS-GC-MS AC: CNTs, 157.34 mg g-1 [140]
Recovery: 96.8-102
Toluene G-PhAPTMS,- SGEP GC-FID Removal efficiency:> 95% Air [140]
GC-MS Adsorption: Chemical and physical
Flow rate : 200 ml min-1
Temperature: 40OC
benzene copper oxide HS-GC AC for benzene: 100.24 mg g-1 Water [142]
toluene nanoparticles (CuO- AC for toluene: 111.31 mg g-1
NPs) Adsorption efficiency : 98.7% for
benzene
Adsorption efficiency : 92.5% for
toluene
VOCs SPME-sol-gel GC-MS LOD: 0.09–0.2 ng mL-1 air [143]
SWCNT / silica Adsorption: 15 min for 25oC
Desorption: 3 min for 280 oC
Formaldehyde SPME PDMS-DVB GC-MS LOD: 0.002–0.032 µg m-3 Air [144]
Adsorption: 15 min for 25oC water
Desorption: 4 min for 250 oC
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- GC-FPD LOD: 1.6–93.5 ng L−1 water [147]
CAR lakes
PBDE DI-SPME MWCNT GCECD LOD: 3.6–8.6 ng L−1 river [148]
Recovery: 90–119% water
OCP HS-SPME GCµECD LOD: 0.16–0.84 ng L−1 Sea [149]
Recovery: 63–127% water
VOCs 3D-SPE-CB-PLA) HPLC r2=0.96 water [150]
Infill print densities: 15 - 50%.
Ambient temperatures : 19.0±0.5 °C
50 Anal. Method Environ. Chem. J. 3 (2) (2020) 34-58

AC: Absorption Capacity methodologies. The human life depends on

GC-MS: Gas chromatography mass spectrometry water future and elimination of pollutions such
GC-FID: Gas chromatography equipped with flame
as VOCs in waters. By growing economy and
ionization detector
SWV: Square wave voltammetry increasing population, the main theme is water
SHS-GC-MS: Head space gas chromatography mass supplies without any contaminations. Quantity and
spectrometry quality of water must be checked daily and main
GC: Gas Chromatography
parameters of waters should be controlled. So,
SOM: Sized Organic Molecules
ROS: Residual organic solvent (ethanol, the water, especially drinking water conservation
tetrahydrofuran, cyclohexane, n-heptane) is extremely important, and contaminations such
D- μ-SPE: Dispersive micro solid phase extraction as BTEX, VOCs and other organic pollutions in
method
waters should be removed by new technologies.
SLS: Solid liquid separation
SE-UOOG: Solvent extraction-Unconventional oil The technologies based on sorbents depend on
ore Gangues water characteristics, affordability, acceptability
CBD-DE: Cathodically pretreated boron doped and level of application. Every methodology for
diamond electrode
VOCs removal from waters have many advantages
LV-LLE: Low volume liquid-liquid extraction
DAI: Direct aqueous injection and disadvantages for water treatment. Therefore,
ASTM: ASTM D-5790 Purge and trap the important parameters for any methodology
G-PhAPTMS- SGEP: Functionalizing graphene with such as speed, simplicity and selectivity must be
N-Phenyl-3-aminopropyl trimethoxy -sorbent gas
studied. The vary methodology such as, solid phase
extraction
HS-GC: Headspace gas chromatograph extraction, liquid phase extraction, the adsorption/
3D-SPE-CB-PLA: 3D printed solid-phase extraction desorption, the sole gel technology, RCO, CO
carbon black modified polylactic acid (PLA) and PCO have been used for VOCs removal from
OCP: Organo chlorine pesticides
waters. In this review the recent technologies based
PBDE: Polybrominated diphenyl ethers ACN:
acetonitrile on sorbents or catalysts are introduced for VOCs
BTEX: benzene, toluene, ethyl benzene, ortho-xylene removal from water samples.
and meta- and para-xylene
BTX: benzene, toluene and xylene
DAD: diode array detector
6. Acknowledgement
DI: direct immersion This review was supported by the Science and
ECD: electron capture detector Research Branch, Islamic Azad University and
FID: flame ionization detector Dr. Hamid Shirkhanloo in Research Institute of
FPD: flame photometric detector
Petroleum Industry of Iran.
FD: fluorescence detection
LOD: limit of detection (µg L−1)
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