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Air ionization as a control technology for off-gas emissions of volatile organic

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Article  in  Environmental Pollution · January 2017

DOI: 10.1016/j.envpol.2017.03.026

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 Environmental Pollution 225 (2017) 729e743

Contents lists available at ScienceDirect

Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Air ionization as a control technology for off-gas emissions of volatile

organic compounds*
Ki-Hyun Kim a, *, Jan E. Szulejko a, Pawan Kumar b, Eilhann E. Kwon c,
Adedeji A. Adelodun d, Police Anil Kumar Reddy a
a
Department of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul, 04763 South Korea
b
Department of Nano Science and Materials, Central University of Jammu, Jammu, 180011 India
c
Department of Environment and Energy, Sejong University, Seoul 143-747, 05006 South Korea
d
Department of Marine Science and Technology, School of Earth and Mineral Science, The Federal University of Technology, P.M.B. 704, Akure, Nigeria

a r t i c l e i n f o a b s t r a c t

Article history: High energy electron-impact ionizers have found applications mainly in industry to reduce off-gas
Received 7 January 2017 emissions from waste gas streams at low cost and high efficiency because of their ability to oxidize
Received in revised form many airborne organic pollutants (e.g., volatile organic compounds (VOCs)) to CO2 and H2O. Applications
11 March 2017
of air ionizers in indoor air quality management are limited due to poor removal efficiency and pro-
Accepted 11 March 2017
duction of noxious side products, e.g., ozone (O3). In this paper, we provide a critical evaluation of the
Available online 27 March 2017
pollutant removal performance of air ionizing system through comprehensive review of the literature. In
particular, we focus on removal of VOCs and odorants. We also discuss the generation of unwanted air
Keywords:
Air pollution control
ionization byproducts such as O3, NOx, and VOC oxidation intermediates that limit the use of air-ionizers
Ionization in indoor air quality management.
Radical © 2017 Published by Elsevier Ltd.
VOCs
Odors
Oxidative destruction

1. Introduction employed for adsorption, absorption, and condensation through

VOCs and odorants pose nuisance and health risks in urban
environments (Kim and Park, 2008). Thus, the chronic presence of
those pollutants in outdoor environments requires effective emis-
sions control strategies on large emission sources (e.g., from in-
dustry). Much research effort has been devoted to the development
of various strategies to eliminate or reduce such pollutants
(Luengas et al., 2015). Recent developments in air cleaning tech-
niques have resulted in significant advances in indoor air quality
(IAQ) control, enabling efficient treatment of diverse chemical
(odorants, VOCs, and PMs) and biological (microbes) pollutants
(Zhang et al., 2011, 2013; Luengas et al., 2015).
Airborne organic matter, such as VOCs, has human health im-
pacts and is the prime cause of poor air quality index (AQI). To meet
AQI standards, concentrations of VOCs can be controlled by either
destructive or non-destructive methods. For the latter, various
porous media with diverse physico-chemical properties can be
* can efficiently convert VOCs into CO2 and H2O. Despite the good
This paper has been recommended for acceptance by Charles Wong.
* Corresponding author.
E-mail address: kkim61@haynyang.ac.kr (K.-H. Kim).
which VOCs can be captured, either for recovery or for subsequent
thermal destruction. However, these techniques have both advan-
tages and disadvantages. For example, a broad array of VOCs has
been treated using sorbents such as activated carbon or zeolites
(Zhang et al., 2013). However, to adequately maintain their treat-
ment efficiency, sorbents need to be replaced or regenerated at
regular intervals taking into consideration the specific break-
through time of each VOC. Liquid-phase solvents (such as water and
organic solvents) have also been employed as sorption media to
capture VOCs depending on their solubility. The VOCs can then be
recovered and/or regenerated by solvent distillation, but this is an
energy-intensive process. Condensation technology can be used to
treat highly concentrated VOC streams. The major drawbacks of
these non-destructive methods are the need for post-treatment,
and the requirement to clean-up spent materials such as the solid
adsorbent (zeolite or activated carbon) or liquid solvent waste.
Destructive methods for the removal of VOCs commonly involve
thermal oxidation with or without a catalyst. Oxidative methods
performance of thermal destruction methods, they tend to
consume a large amount of energy. Although catalytic oxidation is

http://dx.doi.org/10.1016/j.envpol.2017.03.026
0269-7491/© 2017 Published by Elsevier Ltd.
730 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743
feasible economically, catalyst poisoning can occur due to the
production of undesirable byproducts (e.g., sulfur, phosphorus, and
halogenated compounds). Biofiltration is a cost effective and eco-
friendly alternative relative to conventional techniques. Nonethe-
less, it has also been found to suffer from several drawbacks (e.g.,
poor mass transfer from gas to biofilm, inability to separate soluble
VOCs, and the release of dust/microorganisms in the process)
(Luengas et al., 2015).
In recent years, air ionization methods have been proposed and
investigated intensively for the treatment of diverse VOCs and
odorants. In this review, we provide insights into fundamental as-
pects of this new, rapid, green, low-cost, synthetic, and potentially
effective strategy for air quality remediation. To assess the role of
air ionization methods for the air quality control, we evaluate the
performance of these methods relative to conventional techniques.
Last, we discuss future opportunities for air ionization techniques
as reliable tools for controlling VOCs and odors to meet air quality
standards. In addition, limitations of air ionization techniques,
particularly the release of unwanted byproducts (e.g., NOx and O3)
during the treatment of VOCs, are discussed.
2. Conventional methods for VOC removal
In this review, we place great emphasis on air ionization
methods for removal of VOCs. However, there are diverse ap-
proaches that can be taken. As summarized in Table 1, conventional
approaches to remove VOCs fall into three categories: (a) physical
(sorbent adsorption, solvent adsorption, membrane separation and
condensation), (b) chemical (chemical scrubbers, thermal inciner-
ation, and catalytic oxidation), and (c) biological (bioscrubbers and
biofiltration) methods. The performance of these conventional
techniques with regard to VOC removal is described briefly below.
To assess whether commonly-used fan-driven cleaning tech-
nologies improve air quality, a panel of experts investigated a total
of 59 of 26,000 screened articles (Zhang et al., 2011). The efficiency
of air cleaning devices was assessed in terms of clean air delivery
rate (CADR), which is defined as the product of single-pass removal
efficiency and space velocity through the device. The most effective
technologies were particle filtration and sorption of gaseous pol-
lutants. However, none of the reviewed technologies (catalytic
oxidation, filtration, ozone oxidation, plasma, sorption, or UV
destruction of microorganisms) was effective at removing most
pollutants, while many of them were found to generate undesirable
products.
The cost of various conventional VOC control techniques was
estimated with reference to high-energy electron beams (Son et al.,
2010). The ranges of annual costs (per cubic foot per minute (cfm))
for various methods were 25e120 USD (absorption; product re-
covery can offset operating costs, but requires rigorous mainte-
nance), 10-35 USD (adsorption, activated carbon, product recovery
may offset operating costs, moisture sensitive, some compounds
can clog pores, e.g., aldehydes, ketones, and esters), 15-75 USD
(biofiltration, less initial investment, less secondary waste, slow,
selective microbial VOC, removal), 20-120 USD (condensation,
product recovery may offset operating costs, requires rigorous
maintenance), 15-90 USD (catalytic oxidation, possible energy re-
covery (up to 70%), sensitive to operating conditions), 15-150 USD
(flaring, possible energy recovery (up to 85%), halogenated com-
pounds may need additional equipment), 15-40 USD (zeolite,
effective up to 90% relative humidity, product recovery offsets
operating costs, high zeolite cost and limited availability), and 15-
30 USD (membrane separation, no further treatment, solvent re-
covery may offset operating costs, membranes are rare and costly).
The removal efficiencies of these approaches are generally in the
range of 60e99%.
2.1. Physical methods
The physical removal of airborne VOCs is based on VOC parti-
tioning between the gas-phase (air) and some other phase (e.g.,
sorbents (either liquid or solid), transport through membranes, or
the VOC condensed phase). For sorbent-based removal, it is
essential to consider and evaluate the following factors: partition-
ing coefficient, sorbent capacity, breakthrough time and volume,
and sorbent regeneration (Wells, 2003). Using adsorption tech-
niques, VOCs can be removed from the air stream by physical
adsorption onto porous medium like silica gel, alumina, activated
carbon, zeolites, and MOF, among other materials (Vellingiri et al.,
2016; Kabalan et al., 2016; Zhu et al., 2016; Yang et al., 2013).
However, adsorption techniques are limited by the need for post
treatment to dispose of spent adsorbents and/or to treat the
adsorbed VOCs, which increases the cost of treatment.
The use of liquid solvents (usually water, mineral oils, or pe-
troleum oils) to strip VOCs from air streams through contact with
the contaminated air results in removal efficiencies of 95e98%
(Heymes et al., 2006; Ozturk and Yilmaz, 2006; Tatin et al., 2015).
Despite the efficiency of VOC treatment, however, absorption has
some disadvantages like the presence of insoluble VOCs and/or
need for post-treatment of the absorbent liquid. Condensation
based on non-destructive separation allows recovery of VOCs from
the air stream in a liquid state with efficiencies as high as 99% (Shi
and Huang, 2014). Nonetheless, a very low (cryogenic) condensa-
tion temperature is often required to accomplish the capture of
targets (in the condensed phase) from the air stream. In addition,
this method is only efficient when the concentration of VOCs in the
air stream is very high (>1% v/v or > 10,000 ppm) (Gupta and
Verma, 2002).
2.2. Biological methods
Using biological processes, a wide range of pollutants can be
digested into less toxic and odorless compounds. In general, bio-
logical processes can be divided into biofiltering processes and
bioscrubber processes. The latter involve absorption of contami-
nants in aqueous media followed by biological treatment (Koutinas
et al., 2007; Potivichayanon et al., 2006; Nielsen et al., 2007). Bio-
scrubbing methods are easily controllable and allow removal of
products by washing out to avoid inhibitory effects. However, when
attempting to remove less soluble or hydrophobic VOCs (e.g.,
methane, hexane, toluene, and benzene), limited mass transfer may
be problematic (Nikiema et al., 2005; Mun ~ oz et al., 2007). This
might be one of the reasons why bioscrubbing is less commonly
used than biofltration.
Biofilters are another type of short-contact bioreactor. Here,
moist, polluted air is flowed over a porous bed of immobilized
microorganisms to remove VOCs (Hwang et al., 2008; Torretta et al.,
2015; Wang et al., 2009; Steinberg et al., 2005). The removal effi-
ciency of VOCs by biofiltration is limited by mass transfer of target
pollutants and the microbial metabolisms specific for target pol-
lutants. Thus, the packing materials need to be changed frequently
to enhance the performance of the system, and there may be
incomplete removal of VOCs.
2.3. Chemical methods
Processes based on chemical scrubbing and thermal oxidation
(with/without catalyst) are commonly categorized as chemical
treatment methods. Chemical scrubbing is the most common
method used to remove airborne pollutants, especially odors and
VOCs. Acidic or alkaline solutions (e.g., sulfuric acid and sodium
hydroxide (caustic soda)) are used as scrubbing media. To oxidize
 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743 731

Table 1
Comparison of the performance of conventional methods employed for the treatment of airborne VOCs.

Type of treatment Target VOCs Removal Remarks References

efficiency (%)

A. Physical Methods
Absorption Toluene, benzene, 1, 90e98  Product recovery can offset operating costs Jeon et al., 2008;
2-dichloroethane,  Careful maintenance is required Bay et al., 2006;
and acetone  Requires pre-treatment of VOCs
 Most VOCs are water insoluble, thus have reduced absorption
efficiency
 Solution after absorption needs to be disposed of

Adsorption Benzene, toluene, 80e90  Recovery of compounds may offset annual operating costs Zhu et al., 2016;
(activated carbon, dichloromethane/  Vulnerable to moisture; some compounds like ketones, Tian et al., 2016
activated alumina, trichloromethane, aldehydes, and esters clog the pores and decrease efficiency Kabalan et al., 2016
silica gels, n-hexane  Secondary pollution may arise during the process of
zeolites, etc.) desorption
Condensation Toluene, octane, 70e85  Product recovery can offset operating costs Belaissaoui et al., 2016;
acetone, propane,  Requires careful maintenance Uria-Tellaetxe et al., 2016
ethane,
ethylene, naphthalene
B. Biological methods
Biofiltration Limonene, 60e95  Requires less initial investment, less non-harmful secondary Steinberg et al., 2005;
chlorobenzene, waste, and non-hazardous Wang et al., 2009;
toluene  Slow, and selective microbes decompose selective organics, Matteau and Ramsay, 1999
thus requires mixed cultures of microbes
 Requires a large area and a long start-up time
Biological scrubbers Benzene, hydrogen 90e99  Biological scrubbers are low maintenance and require little Nielsen et al., 2007;
sulphide, 1, operator attention Potivichayanon et al., 2006;
2-dichloroethane and  Gaseous pollutants have to be dissolved in aqueous Phase, Koutinas et al., 2007
fluorobenzene which may result in gas transfer problems
 These systems produce musty or earthy odors, which
depending on the proximity of the receptors, may require
additional refining
C. Chemical Methods
Catalytic oxidation Benzene, ethylacetate, 90e98  Efficiency is sensitive to operating conditions Papaefthimiou et al., 1998;
toluene  Susceptible to impurities Azalim et al., 2011;
Saqer et al., 2011
Thermal oxidation Benzene, toluene and 95e99  Halogenated and other compounds may require additional Choi and Yi, 2000
xylene control equipment
 Noxious gases are released
Chemical scrubbers Resorcinol, dimethyl 90e99  Widely used to treat odors in wastewater treatment facilities Biard et al., 2011;
(NaOCl, NaOH, NaHCO3, sulfoxide,  Efficient removal of various contaminant types and oxidation Wu and Lee, 2004
aqueous NH3 etc.) dimethyl sulfide of H2S
 Requires significant level of supervision and maintenance

hydrogen sulfide and other reduced sulfur compounds, chemicals
like sodium hypochlorite (bleach) are typically used in liquid so-
lutions. Thermal oxidation results in conversion of VOCs into
complete oxidation products such as CO2, H2O, NOx, and SO2,
depending on their chemical compositions (Salvador et al., 2006;
Choi and Yi, 2000).
To address the energy-intensive nature of thermal oxidation,
catalytic oxidation has been proposed to enhance the destruction
efficiency of VOCs at moderate temperatures. For the catalytic
oxidation of various VOCs, a number of catalysts (supported noble
metals, binary oxides, solid solutions of metal oxides, doped metal
oxides, etc.) have been fabricated and commercialized (Bastos et al.,
2009; Papaefthimiou et al., 1998; Saqer et al., 2011; Azalim et al.,
2011). The main disadvantage of catalytic oxidation is catalyst
poisoning (i.e., deactivation) caused by the release of hazardous
components (e.g., sulfur and halogens) into the air stream.
2.4. Photocatalytic oxidation (PCO) for VOC removal in indoor
environments
In the past decades, the well-established and widely-studied (by
both academia and industry) photocatalytic oxidation (PCO) has
been applied for indoor air quality management (Mo et al., 2009;
Mamaghani et al., 2017; Demeestere et al., 2007). Detailed discus-
sion on PCO is beyond scope.
3. Mechanisms of engineered air ionization
Air ionization systems are operated by flooding the atmosphere
with positive and negative ions. Electrostatic charge represents the
accumulation of ions of a particular charge on a non-conducting
surface until a steady-state is attained through neutralization
(Stalker and Richard, 1988). Natural ionization sources include
electromagnetic radiation (e.g., cosmic rays, gamma rays, light-
ening, and solar ultraviolet radiation) and alpha/gamma radiation
from radioactive materials in the Earth's crust (Jokl, 2002).
Gas molecules are electrically neutral under STP conditions. The
minimum amount of energy needed to ionize gas-phase molecules
and atoms is known as the first ionization energy (IE) (Middleton,
1989; Sawant and Jadhav, 2012). If the ionizing energy is enough,
then one or more bound electrons can be stripped from the
molecule (or atom) into the gas phase as free electrons to yield
molecular cations with single and/or multiple charges. These pri-
mary positive ion species can undergo sequential ion-molecule
reactions with polar neutral water molecules to yield protonated
water cluster ions (e.g., Hþ(H2O)4, m/z 73), as observed in high
pressure mass spectrometry (Szulejko et al., 1992).
Both the natural and anthropogenic pathways for ion formation

are explained schematically in Fig. 1 (Cernecky and Valentova,
2012; Honer, 2010). Excited air molecules (N*2 and O*2), generated
during the ionization process can propagate O3 by chain reaction
732 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743

with NOx products (Dvorak and Koryta, 1983; Fischer et al., 1983;
Sitar, 2006). O3 is a strong oxidizing reagent, which provides a
favorable environment for the destruction of VOCs, even at ambient
temperature (Obulana and Hostin, 2012; Sitar, 2006; Weschler,
2000).
3.1. Mechanisms of air ionization
Basically, an intense electrostatic field around a sharp point will
initiate the electrical discharge of high-energy electrons (Steinman,
2006). These energetic electrons will interact with neutral air
molecules to generate either excited neutral air molecules or pri-
mary positive ions (and additional (slow) secondary electrons).
These slow secondary electrons are quickly thermalized and un-
dergo termolecular electron attachment to O2 to yield the super-
oxide anion (O 2 ) in a parallel plate free-air ionization chamber
(Takata, 2010) (Fig. 2).
Positive and negative ions are continuously generated by an
intense electrostatic field, and quickly reach a steady-state density
(e.g., typically 105 to 106 ions cm3) via ion-ion and ion-electron
recombination reactions. Both electrostatic and ionizing radiation
can be used to produce both positive and negative ions. There are


Fig. 1. Schematics of both (a) natural and (b) anthropogenic pathways for ion particle formation (Cernecky and Valentova, 2012; Honer, 2010).
 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743
numerous methods to create weak bipolar air plasma. No single
ionization method is yet regarded as being the most suitable option

for all situations (Cernecky et al., 2015). Because ion migration is
governed by electric fields and bulk air mass flow, the effectiveness
of an ionization system is highly contingent on various parameters
such as environmental conditions, the problem to be solved, and
the nature of the work (Levit and Beyer, 2011). In addition, another
critical factor to consider is the ionization source for the system,
e.g., high-energy electron impact, AC, DC, pulsed DC, alpha particles,
or X-rays. However, electric field ion sources are not capable of
producing sufficient ions for air quality control purposes. Thus,
stronger ionization sources such as ionizing radiation (e.g., alpha
particles) and corona ionization are used preferentially to generate
higher steady-state ion densities.
3.2. Alpha particle-based and corona ionizers
Air ionization can be achieved by many routes: heavy particle
impact, electron impact, thermal ionization, photon impact, and
electric field ionization (Loeb, 1965; Aleksandrov et al., 2001;
Anikin et al., 2001; Chernikov et al., 2001). The operational mech-
anisms of the two most widely used types of ionizers (alpha
particle-based and corona ionizers) are further appraised as
representative case studies.
First, alpha (a) particles (helium nuclei) are considerably heavier
than other radioactive decay particles (e.g., b or g particles) (Levit
and Beyer, 2011). For that reason, a particles transfer much more
slowly than b-particles of the same energy. At such reduced speeds,
their electric fields can interact for a comparatively extended time
with a molecule's electron cloud to affect energy transfer for an
ionization event. Thus, air has greater stopping power (shorter
mean free path) for a particles than b-particles. Helium nuclei
emitted from Po210 with an estimated translational energy of
5.4 MeV have a mean free path of only ~4 cm in air at 1 atm (Levit
and Beyer, 2011). Each a particle creates approximately 250,000
ion-electron pairs in 4 cm. Because b particle ionization results in
substantially lower ion density due to its much lower stopping
power, it should be less effective at maintaining static charge. Each
ionization event creates an equivalent number of positive and
negative charges (e.g., N2 / Nþ 2 þ e; 1 positive molecular ion and
Fig. 2. A parallel plate free-air ionization chamber (Takata, 2010).
733
one free electron). Therefore, a particle-based ionizers generate an
almost charge-balanced population of positively and negatively
charged species without the need for additional ion or electron
sources to maintain charge neutrality. The merits of a particle-
based ionizers include low flux of a particles, high temperature
plasma generation, and reduced concentrations of free radicals/
cluster ions (Shiue et al., 2011).
Although air ionization is conventionally generated by coronas
from needle electrodes, unwanted particles can also be generated
(Shale et al., 1964; Wilson and Brewer, 1973; Vinogradov et al.,
2001). To circumvent this shortcoming (i.e., develop clean ion-
izers), a number of conditions/parameters (e.g., choice of electrode
material, sharpness, voltage levels, and wave forms of high voltage
signals) have been investigated extensively (Aleksandrov et al.,
2001; Levit et al., 2000; ION, 2010; Shiue et al., 2011). To generate
air ions, needle electrodes are operated at high voltages (usually 10
~ 20 kV DC or AC) (Yost, 1989).
Among such alternative options proposed or developed, corona
ionizers create both neutral and charged species via two mecha-
nisms: (i) erosion of the emitter tip and (ii) plasma formation at the
needle tip. In the case of the latter, the needle tip acts as a chemical
reactor to convert airborne molecular contaminants (AMCs) to
small aerosols which, in turn, agglomerate into larger ones (the
second effect) (Levit and Beyer, 2011). Generally, the cleanest ion-
izers (most erosion free) are the ones that run at the lowest power
output. Optimum configurations are those that avoid recombina-
tion of positive and negative ions so that sufficient ions are received
at the charged object while minimizing the power dissipated at the
emitter tip (Wilson, 1987; Gefter, 2008).
4. Types of air ionization approaches for VOC removal
4.1. Air ionization by thermal plasma
To generate plasma, various types of discharges are employed:
(a) electron-beam (Son et al., 2010; Sun and Chmielewski, 2012), (b)
dielectric barrier (Liang et al., 2015; Jin et al., 2016), (c) pulsed
corona (Grabarczyk, 2001; Nagato et al., 2006), (d) microwave (Cha
and Carlisle, 2001; Wang and Wang, 2016), (e) gliding arc (Bo et al.,
2008), and (f) radio frequency (Yuan et al., 2011; Eliasson and
734 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743
Kongelschatz, 1991) discharge. Air ionization by thermal plasma
involves striking a plasma flame at atmospheric pressure using
high discharge power (P z 1 kW to 50 MW) at high voltage. High
voltage discharge excites gaseous molecules to generate highly
reactive species such as ions and radicals (Hammer, 1999). The
plasma temperature varies from a low of 1000 K to peak temper-
atures of 10,000 to 20,000 K depending on such variables as the
electric voltage, flow rate of the gas, and plasma source (Fridman
and Kennedy, 2011).
High electrical voltage together with an elevated temperature
expedites the production of high fluxes of reactive ions or radical
species, resulting in the destruction of VOCs in a short response
time (Bahri and Haghighat, 2014). As such, the advantages of
thermal plasma include high specific activation and total frag-
mentation of molecules. Nonetheless, practical use of thermal
plasma is restricted by its high operational cost (Heberlein and
Murphy, 2008). Furthermore, because particles in thermal plasma
(electrons, ions, atoms, and molecules in the background gas) are in
thermal equilibrium, overheating of the reaction media is un-
avoidable. Although thermally-induced plasma is effective at
treating high concentration of VOCs, it is not economically viable
for treatment of low concentrations of VOCs. Therefore, this
approach is not economically feasible for treating indoor air, which
generally has low pollution levels.
4.2. Air ionization by non-thermal plasma
Non-thermal (non-equilibrium) plasma (NTP) generated at
ambient pressure is another approach for the generation of air ions.
NTP generates electrons with high-energy and short residence time
capable of initiating destruction of VOCs at ambient temperature
(Xiao et al., 2014; Hołub et al., 2014; Stasiulaitiene et al., 2016). The
destruction of low concentrations of VOCs in high volume streams
by NTP is an important advantage of this approach. However, there
is insufficient number of studies to definitively determine the
mechanism and removal efficiency according to compound class.
A variety of NTP reactors have been developed to treat VOCs. The
different non-thermal plasma techniques are shown in Fig. 3. Air
ionization by non-thermal plasma has been employed to remove
VOCs. However, high power consumption and the production of
undesired by-products (e.g., aldehydes, alcohols, acids, aerosols,
particulate matter, and non-volatile C-containing compounds) limit
the practical application of this technique. To improve the efficiency
of non-thermal plasmas, the residence time of VOCs in the plasma
zone can be increased. A combination of NTP and heterogeneous
catalyst (BaTiO3, TiO2, Fe, Co, Cu, Ni, Mn oxides, Ag, Au, Pt noble
metal supported porous silica, alumina or zeolites) thus appears to
be a feasible alternative. An increase in the residence time of
adsorbate molecules in the plasma zone can lead to considerable
improvement in conversion rates (>99%) and superior selectivity
(>60%) towards total oxidation products, e.g., CO2 and H2O (Ghaida
et al., 2016; Kim et al., 2010; Rousseau et al., 2005).
4.2.1. Reactors without catalyst beds
The decomposition characteristics of BTX (prepared at 300 ppm
in synthetic air) were investigated after DC corona discharge at
atmospheric pressure (Satoh et al., 2012); the experimental setup
and results were very similar to those described below in this
paragraph (Sakai et al., 2016). Major decomposition products were
CO2, CO, HCO2H, and (CHO)2O while C2H2, HCN, and (CHO)2 were
found as minor products. It was thus concluded that the BTX was
converted to CO2 through diverse intermediates, e.g., CO, HCO2H,
and others. Likewise, the decomposition of 300 ppm BTX (in 20/80
O2/N2 synthetic air) was also measured after DC corona discharge in
a 9.4 L reactor (10 cm radius, 30 cm height) under static conditions
at atmospheric pressure (Sakai et al., 2016). Decay rates of benzene
and toluene were ~1.7 and 2.7 h1, respectively, at a power of 5.5 W
and discharge voltage of 27.5 kV. Using a mass change tracking
(MCT) approach, the carbon budget was estimated after 1 h of re-
action against 300 ppm (or 2100 ppmC) toluene. Toluene was
significantly reduced to 75 ppmC (96% removal) and several reac-
tion products such as CO2 (510 ppmC), CO (370 ppmC), and formic
acid (340 ppmC) were identified, along with other identified
products (210 ppmC) and unaccounted-for products (600 ppmC,
largely non-volatile deposits inside the reactor). The removal effi-
ciency for benzene, toluene, and xylene was 0.8, 1.5, and 2.2 g
kWh1, respectively. The large amount (370 ppm) of CO generated,
however, was disturbing. The destruction efficiency of toluene was
also tested by irradiating the model toluene-air gas-mixtures with
an ILU-6 accelerator at the Institute of Nuclear Chemistry and
Technology (INCT), Poland (Sun et al., 2009). Accordingly, the
decomposition efficiency of toluene increased with absorbed dose
while decreasing with its initial concentration. At the initial 32 ppm
toluene level, the decomposition efficiencies were greatly distin-
guished between 50% (14.5 kGy dose) and 93.8% (58.0 kGy dose)
with benzaldehyde as one of the major by-products.
The removal of toluene (14.7 ppm), 1.5-hexadiene (13.3 ppm),
and chloroform (19.5 ppm) by negative air ions (mainly O 2 ) was
explored using a lab-scale negative air ion (NAI) reaction chamber
under static conditions (Wu and Lee, 2004). The stainless steel NAI
chamber (id ¼ 39 cm, l ¼ 78 cm) had three discharge electrodes,
each consisting of an array of 20 needles with a tip of 0.1 mm in
diameter with discharge voltages of up to 30 kV. The concentra-
tions of reaction products (O3, NO, and NO2) were voltage depen-
dent, and were therefore not detected below 17 kV. Hence, removal
experiments were carried out at 15 kV. The NAI concentration was
about 1.3Eþ06 ions per cm3, while no positive ions were detected.
Removal efficiencies after a 12 h reaction (0% RH air) were 13% for
toluene, 8.1% for chloroform, and 98% for 1,5-hexadiene. No reac-
tion products were detected by GC-FID for toluene and chloroform;
1,5-hexadiene gave an intermediate product (4-pentenal) that
reached a maximum concentration (~2 ppm) at 7e10 h and
decayed to ~0 ppm by 16 h (Fig. 1S).
The decay of benzene (initially 106 ppm) and toluene (initially
112 ppm) inside a closed 0.71 m3 chamber (with a 4.6 m3 h1 fan)
was studied under two conditions: (a) natural decay and (b) with
an air ionizer that generated ~175,000 ions cm3 inside the
chamber (Cho et al., 2012). The natural (kn) and air ionizer decay
(ka) constants were virtually identical, showing that air ionization
had a minimal impact. The average kn and ka values (three mea-
surements) for benzene were 1.29 and 1.40 hr1, respectively. The
corresponding toluene kn and ka values (two measurements) were
1.30 and 1.39 hr1, respectively.
4.2.2. Catalyst packed beds
In a companion article, Van Durme et al. (2007b) installed a
catalytic packed-bed reactor (either post plasma {PPC} or in-plasma
{IPC}) in their lab-built non-thermal plasma reactor to study the
removal of 0.5 ppm toluene (Fig. 4). Two catalysts were used: the
commercial catalyst Aerolyst® 7706 TiO2 with 15% Al2O3, and the
O3-degrading catalyst CuOMnO2/TiO2. The residence time in the
reactor was 1.12 s at a flow rate of 10.8 L min1. Catalyst (10 or 15 g)
was loaded on either the IPC or PPC bed for evaluation. Nearly 80%
of toluene was removed when 10 g of CuOMnO2/TiO2 (PPC) was
used vs. ~0% in the absence of catalyst at an energy dose of ~2 J L1
(1.7 kGy) and flow rate of 10.8 L min1 (Fig. 2S). Performance of the
Aerolyst® 7706 catalyst was inferior to that of CuOMnO2/TiO2; an
energy dose of 15 J L1 (12.9 kGy) was needed to achieve 80%
removal (IPC). No plasma degradation products of toluene were
detected by SPME/GC/FID. Outlet emission levels of ozone and NO2
 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743
Fig. 3. Schematic of different non-thermal plasma reactors for generating air ions (Vandenbroucke et al., 2011; Kim, 2004; Urashima and Chang, 2000; Vitale et al., 1996; Yardimci
et al., 2000; Zoschke et al., 2012).
were much reduced with catalyst, e.g., O3 (14 ppb) and NO2
(2520 ppb (no catalyst) vs. 550 ppb (PPC, 13 kGy)). No catalytic
deactivation was observed over 48 h of continuous operation. If
scaled up to 30 m3 room, the plasma catalytic hybrid reactor needs
an air processing rate (APR) of about 500 L min1 to treat a room in
a reasonable amount of time (~1 h for 80% removal of 0.5 ppm
toluene); plasma power input would need to be ~150 W (at 15 J L1
dose) or 0.75 g kWh1 at 45 kV discharge.
4.2.3. Relative humidity
Use of non-thermal plasma (DC positive corona discharge) to
remove toluene from indoor air has also been explored (Van Durme
et al., 2007a). An inlet air stream containing toluene (0.5 ppm) at
1 atm pressure was flowed through a lab-scale non-thermal plasma
reactor at 10 L min1. Toluene removal, when examined under
three RH conditions (0, 26, and 50%), was about 80% for an energy
dose of 60 J L1 (or ~50 kGy). In contrast, ozone concentrations at
the outlet were dependent on the energy dose and RH, with levels
of ~300 ppm in dry air (0% RH) relative to 150 ppm (60% RH)) at a
dose of 75 J L1. A large number of toluene-derived products (e.g.,
formic acid, benzyl alcohol, and 4-methyl-2-propylfuran) were
observed by GC-MS after treatment of air containing 150 ppm
toluene (<1% RH, 10.8 L min1 flow, and 54 J L1 dose); these by-
products may be even more hazardous than toluene (Fig. 5). A
degradation pathway for toluene was proposed (see Fig. 6, bottom
panel).
Oxidation products of organic compounds (e.g., toluene, i-oc-
tane, and halogenated methanes) in atmospheric air corona
plasmas have also been examined (Marotta et al., 2010). A corona
discharge reactor operated with DC (±25 kV) or pulsed current was
735
built as a grounded stainless cylinder (38.5 mm id and 600 mm
long) with a 1 mm wire electrode along the axis (Schiorlin et al.,
2009). Removal efficiencies (kE) of this reactor were reported in L
kJ1 with the flow rate through the reactor at 0.45 L atm min1. The
analyte concentration [A] can be expressed as [A] ¼ [A]0.exp(-
kE.SIE), where [A]0 is the initial concentration and SIE is the specific
input power (SIE) in kJ L1. The kE value was higher in humid air
(40% RH) than dry air (eDC discharge). For example, the kE values
for 500 ppm toluene were -DC 0.42 (dry air) and 0.81 (44% RH)
and þDC 0.14 (dry air) and 0.13 (40% RH). A positive ion APCI mass
spectrum of blank air showed various hydrated species, e.g.,
H3Oþ.(H2O)2 (m/z 55, base peak) and NOþ.(H2O)2 (m/z 66); for
hexane and i-octane, various CnHþ2nþ1 species were noted whereas
for toluene, protonated toluene (m/z 93) was dominant. A number
of products (e.g., H2O, CO2 (major), N2O, CO, HCO2H, HNO3, and O3)
were detected in the reactor outlet by FTIR after -19 kV DC corona
treatment of air containing 500 ppm toluene.
4.3. Air ionization by dielectric barrier discharge (DBD)
Dielectric barrier discharge (DBD) is an electrical discharge
system that creates non-thermal plasma between two electrodes
separated by an insulating dielectric barrier operated at high
voltage. The conversion of 2-heptanone by the DBD plasma method
was explored under different pulsed modes of excitation, energies,
and carrier gas compositions (Chiper et al., 2010). These authors
observed that the removal efficiency was 30% higher when 2e3% of
oxygen was added to nitrogen than in pure nitrogen. PMs were
observed in the plasma due to nucleation of dehydrogenated VOCs
(e.g., polyaromatic hydrocarbons and hydroxides) (Borra, 2006;
736 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743
Fig. 4. Schematic of hybrid plasma catalytic system for efficient toluene removal
(reproduced from Van Durme et al., 2007b).
Zhang et al., 2013). As the exposure to this particulate matter can
pose human health problems, concurrent removal of VOCs along
with the generated particulate material is a matter of great concern
(Donaldson et al., 1998). Jin et al. (2016) investigated the decom-
position of n-hexane in a DBD reactor filled with different kinds of
dielectric balls (quartz, less porous, and porous alumina balls); the
DBD reactor filled with porous alumina balls was efficient at
reducing particle emission by adsorbing liquid particles. Further,
the DBD method, when combined with photocatalysis, consider-
ably improved VOC removal efficiencies (Palau et al., 2015; Ghaida
et al., 2016).
4.4. Pulsed corona discharge
Pulsed corona discharge is another means to produce NTP to
treat VOCs in air streams. In corona discharge, a current flow from
an electrode at high potential can ionize a neutral fluid such as air
(surrounded by electrode) so as to create a region of plasma around
the electrode. The ions generated in bulk gas can thus effectively
participate in degradation of VOCs in the air stream. There are two
types of corona discharges - positive and negative corona discharge
- that result in the production of positive and negative air ions,
respectively. The degradation of i-octane and hexane was investi-
gated using positive and negative coronas (Marotta et al., 2008).
These authors reported that a radical mechanism was dominant in
negative DC corona ionization, whereas ionic reactions prevailed in
positive DC corona ionization.
The oxidative degradation of toluene and limonene (ppm level
at large air flows) was studied using a hybrid pulsed corona reactor
(Hoeben et al., 2012). The conversion efficiencies of those two
compounds to biocompatible carboxylic acids (e.g., acetic and for-
mic acids) were 74% and 81%, respectively. A simplified mechanism
for the degradation of toluene and limonene using ozone as an
oxidant is illustrated in Fig. 6 (upper panel) (Hoeben et al., 2012).
Microwave-induced plasma is another method capable of
generating electrode-less discharges to produce air ions. In this
approach, high frequency (GHz) radiation is used to create gas
discharges. The technical advantages are low power consumption
as well as production of high ion concentrations in stable plasma,
even under humid conditions (Cha and Carlisle, 2001). Cha and
Carlisle (2001) investigated the removal and destruction of chlo-
rinated and non-chlorinated solvents extracted from soil vapor.
They demonstrated that microwave ionization performed better
than conventional thermal/catalytic processes used for VOC con-
trol. Kim et al. (2014) developed an atmospheric-pressure micro-
wave plasma in a reverse vortex reactor to remove VOCs from
polluted air streams. These authors focused on the destruction of
VOCs in high flow rate polluted streams as generated in industry. A
destruction removal efficiency (DRE) of 98% was achieved for gases
containing 550 ppm of VOC at an air flow rate of 5 m3 atm min1.
4.5. The electron impact method
We consider the electron impact method one of the most so-
phisticated and novel technologies for treatment of flue gas emitted
from diverse sources (e.g., coal-, lignite-, or heavy fuel oil-fired).
However, the electron guns used to produce high-energy elec-
trons are very large (several m3), therefore special radiation
shielding is required. Hence, this method is not suitable for small-
scale indoor air applications, as the electron gun is operated only
under vacuum; the high-energy electron beam needs to pass
through a window interface into the air stream. When used to treat
VOCs at low concentration and high volumetric flow, electron beam
irradiation can produce free radicals and ions in a short time span
(i.e., 108e101 s) in the reaction medium (Son et al., 2010). As such,
the EB process has been shown to be most economical for low VOC
concentrations (diluted into high volume flows) with consumption
of about 0.2 kWh of electricity per 100 m3 atm (Hirota et al., 1995).
Energetic electron impact (EI) of molecules can result in the
formation of excited (Rydberg) neutral molecules, leading to
pollutant fragmentation and ionization. Thus, highly reactive free
radicals produced by the EI system initiate chain reactions, result-
ing in the cracking of the larger molecules into smaller species (Alfi
et al., 2015). EI of surrounding air results in the generation of
various primary ions, secondary ions (via by ion-molecule re-
actions), and excited neutrals (such as e, Nþ þ þ þ þ
2 , N , O2 , O , H2O ,
OHþ, Hþ, COþ þ * *
2 , CO , N2, O2, N, O, H, OH, and CO) (Son et al., 2010).
 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743
Fig. 5. GC/MS chromatogram of toluene degradation products produced in a positive DC corona discharge: dry air (<1% RH), reactor flow rate ¼ 10.8 L.min1,
[Toluene] ¼ 150 ± 1 ppm, dose ¼ 54 J.L1 (or ~47 kGy), and reactor inlet pressure ¼ 101.3 kPa (Van Durme et al., 2007a).
The decomposition characteristics of trimethylamine after
electron beam processing were investigated (Son et al., 2013).
Addition of water vapor resulted in a 5e30% increase in the overall
removal efficiency of trimethylamine. This was attributed to the
generation of strong oxidizing -OH radicals by the electron beam
that resulted in the degradation of various air pollutants.
Chmielewski and Ostapczuk (2010) conducted lab-scale experi-
ments using an 800 keV electron beam irradiation system for the
cleanup of the exhaust stream from the burning of the heavy fuel
oil, mazut (partly refined crude oil: ~3% sulfur content). However,
these authors did not provide any details about the total power
consumption or capitalization costs, therefore the industrial cost
effectiveness of this technique cannot be evaluated. The removal of
SO2 and NOx (as (NH4)2SO4 and NH4NO3) was achieved simulta-
neously at 98 and 80% efficiency, respectively, under the following
optimal conditions: 5 m3 atm hr1 stream flow rate, 20 KW electron
beam power (pulse width and frequency not reported), 800 keV
electron energy, 12.4 kGy dose (corresponding to ~20 W irradiating
power and a temperature increase of 17 K at constant volume), and
ammonia/water injection. (NH4)2SO4 and NH4NO3 can be sold as
bulk commodity fertilizer to partially offset costs. In addition,
removal efficiencies of polycyclic aromatic hydrocarbon (PAHs) and
BTX were 42 and 86%, respectively at an electron irradiation dose of
5.3 kGy. This technology can therefore be used for simultaneous
removal of acid gases (SO2 and NOx) and organic (PAH and BTX)
pollutants. Note that 1 Gy corresponds to a dose of 1 J of energy per
kg of matter.
The removal efficiency and products formed during electron
beam (550 keV) treatment of 38 ppm butylacetate and 22.5 ppm
xylene (all isomers) in air (flow rate ¼ 278 L.s1) were determined
(Hirota et al., 1995). Butyl acetate removal efficiency was 65% at a
10 kGy dose and formic, acetic, propionic, and butyric acid products
were formed. The removal efficiencies (at 10 kGy dose) of xylene
(o), xylene (m, p), and ethybenzene were ~85, ~90, and ~70%,
respectively. Xylenes (97 mg C m3 input) yielded a number of
reaction products (as mg C m3): formic (2.5), acetic (6.3), propi-
onic (2.6), and butyric (1.8) acids, products on filter pad (40.6,
largest fraction), CO (5.3), CO2 (6.3), and unreacted xylene (14).
Note that CO2 in air (400 ppm ¼ 196 mg C m3) appeared to be
removed, as the detected amount in the effluent was only 6.3 mg C
m3 (or 13 ppm).
737
4.6. Hybrid air ionization methods
The main drawback of the electron impact beam method is the
formation of undesirable byproducts (ozone, CO, CO2, aerosols, and
other trace compounds such as benzene, aromatic/aliphatic alde-
hydes, ketones, acids, and acetates) (Kim, 2002; Sun et al., 2009).
However, the extent of such problems can be mitigated by the use
of heterogeneous catalysts (Cu, Mn, Pd, Pt metals, V2O5, Mn2O3
oxides, and Pt/Pd supported zeolites/g-Al2O3). Thus, the concurrent
use of electron impact beams and catalysts can minimize the for-
mation of byproducts; such hybrid technology can also improve the
decomposition efficiencies of VOCs (Kim et al., 2010; Jeon et al.,
2008).
A hybrid approach using an electron beam 1% Pt/Al2O3 was used
for VOC decomposition in a hybrid reactor (Kim et al., 2004).
Toluene and styrene were destroyed more effectively using a hybrid
system (with a catalyst bed) than by electron beam irradiation only.
A similar treatment system consisting of a compact-sized electron
accelerator and an ozone decomposition catalyst made of MnO2
was developed and tested for the removal of toluene and xylene
(Hakoda et al., 2010). The performance of this electron accelerator
was then compared before and after the concurrent use of a cata-
lytic bed. Removal of toluene and xylene increased from 60 to 91%
and from 81 to 91%, respectively, as mineralization (i.e., to CO2 and
CO) increased from 42 to 100%. Ighigeanu et al. (2008) developed a
new hybrid technique by combining electron beams, microwaves,
and catalysts. This hybrid system exploited the advantages of the
three component techniques, namely (1) very high efficiency of
conversion of VOCs into intermediate products by -OH radical re-
actions after electron beam use, (2) the ability of microwaves to
produce non-thermal plasma in electrode-less reaction vessels, and
(3) complete oxidation of intermediate products to CO2 and H2O by
the catalysts. These authors compared the performance of this
system as a whole and each individual component. The removal
efficiencies of toluene were superior for the combined system
(92.8%) than individual components of the system (Ighigeanu et al.,
2008).
A number of studies were carried out to evaluate the perfor-
mance of electron beam processing relative to other VOC treatment
approaches. Electron beam processing for many VOCs has been
reported to be highly energy efficient relative to pulsed corona
738 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743
Fig. 6. Simplified oxidative degradation pathways of VOCs: upper ((A) toluene and (B) limonene (Hoeben et al., 2012)) and lower (toluene (Van Durme et al., 2007a)).
(Penetrante et al., 1996). These authors found the net electron beam
energy input into a reactor containing carbon tetrachloride (at
100 ppm) was 9 J L1 compared to 555 J L1 for the pulsed corona
method (a similar trend was observed for benzene and methylene
chloride treatment). In a theoretical industrial setting, treatment of
a 1 m3.s1 gas stream would require the excessive power input of
555 kW if the pulsed corona method were used. Relative perfor-
mance of the electron beam and plasma method was also assessed
in terms of removal efficiencies of ammonia (Son et al., 2013). Gas
residence time was 10 times less for the electron beam process than
plasma. Additionally, energy dose for the electron beam process
was much lower (15 kGy) than the plasma (106 kGy) method. As
such, the former is much more energy efficient than the latter.
Despite such advantages, it is not economically feasible to use an
electron beam process to treat indoor air pollutants. A serious
limitation is that electron beam accelerators involve large setups/
installations (several m long) and require a shielding system from
X-rays (from bremsstrahlung) (Chmielewski, 2007; Chmielewski
and Haji-Saeid, 2004). In addition, accelerators self-shielded up to
300 keV have been proposed for VOC treatments. Thus, while these
processes are suitable for industry (>m3 s1 flow rate), they are not
practical for treating VOCs in indoor environments.
5. Basic characteristics and performance of air ionization
approaches
To date, current technologies for VOC treatment have a number
of disadvantages, e.g., unwanted oxidation by-products, high costs,
and limited processing capacity. Thus, it is essential to develop
more cost-effective and environmental-friendly technologies to
meet the ever-increasing demand for air quality control and man-
agement. Air ionization in the foreseeable future may be an
emerging effective alternative for treating airborne VOCs. In this
section, air ionization is critically reviewed in terms of removal
efficiency, throughput, limitations, and cost.
Recent developments in the design and operation of air ioni-
zation devices have made these devices more reliable and efficient
alternatives to treat VOC and odors than conventional methods
(Bohlen and Bozoo, 2009; Karim, 2015). Engineered air ionization
devices are capable of producing specific ions, including reactive
oxygen species (e.g., O3 and O*2), in a controlled manner with
minimal byproducts. Air ionization has been adapted to remove
airborne pollutants including dust particles, secondary organic
aerosols, microorganisms, and allergens from air streams in indoor
environments (Liang et al., 2012). The use of ionization has
 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743
Fig. 6. (continued).
advantages over other removal techniques due to its lower energy
costs, reduced formation of dangerous byproducts, and several
potential health advantages (Daniels, 2001).
A number of strategies that have been developed to generate air
ions to treat VOCs and odors are presented in Table 2. Note that
each method has advantages and disadvantages, and most studies
have been conducted under different experimental setups and
conditions. Hence, it is a challenging task to assess the relative
performance of the different methods. Nonetheless, the perfor-
mance of hybrid technologies appears to be superior to that of in-
dividual methods. In summary, air ionization generates low m/z air
ions, including superoxide anions (O2 -), that can react readily with
airborne VOCs and odors.
Key parameters of air ionizers and other techniques in air
quality management are compared in Tables 1 and 2. We discussed
the significance of air ionization chemistry and its potential for the
advancement of air quality management based on a review of the
current literature (e.g., Daniels, 2001). However, researchers
around the world are continuing to investigate new air ionization
739
applications for both industrial processes and biological systems.
There are several challenges for air ionization techniques that have
to be overcome (Table 3). Further studies are needed to optimize air
ionization techniques to increase process efficiency and reduce
energy requirements to make them cost-effective. We recommend
implementing the following approaches to improve performance:
(i) improve the discharge mode, including the structure of the
reactor and the frequency/voltage of the power supply and (ii)
combine hybrid systems with other approaches (Oda et al., 2002).
6. Conclusions
In this review, we described the fundamental characteristics of
air ionization methods used to improve air quality with respect to
removal efficiency of odors and VOCs. Air ionization technology is
gaining ground as a viable technology for the treatment of specific
VOCs and odors. Air ionization techniques facilitate destruction of
hazardous air/odor contaminates through control of electrostatic
discharges.
740 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743

Table 2
Comparison of performance of different air ionization methods for the treatment of airborne VOCs.

Type of treatment Target VOCs Removal Remarks Reference

efficiency (%)

Electron Trimethylamine 90e98  Formation of by-products Son et al., 2013; Chmielewski

impact beam  Applicable to source high emission rate and/or low and Ostapczuk, 2010
concentration at ambient air temperature and requires
relatively low dose compared to plasma discharge
 Applicable only for pilot plant or industrial scale
treatment of pollutant air streams
Dielectric barrier 2-Heptanone, hexane, 75e99  Low energy efficiency, poor selectivity for CO2 even when Wang et al., 2009;
discharge isovaleraldehyde high conversion rate is reached, and undesirable Kim and Park, 2008
byproduct formation
 Suitable for industrial production, simple operation, and
configuration
Pulsed corona Propene, toluene, 77e99  Higher electron energies and short pulses result in Malik et al., 2005; Jarrige
discharge benzene, n-hexane efficient synthesis of reactive oxygen species for and Vervisch, 2006
efficient oxidative degradation
Microwave 3-Pentanone 98  Low power consumption, production of high levels of Kim et al., 2014
discharge ions, and stable plasma under humid conditions
Thermal plasma Mixture of VOCs 100  High specific activation and total fragmentation of Han et al., 1993; Murphy 2001
pollutants to CO2 and CO

Table 3
Comparison of various principles and approaches employed in air ionization techniques.

Item Method Mechanism Advantages Disadvantages Reference

1. Electron impact (EI) Electron impact Easily regulated and quite Very low energy efficiency. Only a few Son et al., 2010; Sun and
ionization of neutral reproducible electrons penetrate into the air stream Chmielewski, 2012
molecules from the electron beam source.
2. Thermal plasma Gas is heated to Highly efficient and Extremely cost-ineffective and subject Fridman and Kennedy, 2011;
T > 10,000 K to reproducible to matrix contamination. Bahri and Haghighat, 2014
generate a plasma.
3. Photon impact (PI) Photon ionization (UV, Alternative ionization Relatively low efficiency and exhibits Aleksandrov et al., 2001; Anikin
x-rays, g-rays) source and good efficiency adaptability shortcomings when et al., 2001; Chernikov et al.,
at low cost applied to various conditions. 2001
PI ionization cross section about 2e3
orders lower than that required for EI
ionization.
4. Fast ion Hydrogen fusion Fission of heavier atoms Cannot be adapted safely for application Luengas et al., 2015; Son et al.,
bombardment reactions emitting fast releases high energy in many scenarios. 2010; Sun and Chmielewski,
Hþ and Heþ ions at high ions that can cause 2012
MeV translational secondary ionization,
energies to ionize hence, highly productive
neutral molecules
5. Electric field Involves the passing of Considerably high electric Extremely energy intensive. Levit and Beyer, 2011; Luengas
a gas stream between field density (up to a few 
et al., 2015; Cernecky et al.,
highly charged kV/m) is required. Metallic 2015
electrodes electrodes should also have
a sharp geometry for
optimum efficiency. Easy to
generate and controllable

Air ionization technologies based on monopolar and static
electricity discharge have many benefits for air cleaning purposes,
including destruction, transformation, and removal of VOCs and
odors. Namely, they produce fewer hazardous reactants/byprod-
ucts than conventional methods, there is minimal bulk deposition
of odor on room surfaces, and energy costs are low. Air ionization
technologies also have potential health benefits compared to con-
ventional technologies (e.g., filtration and adsorption). Static elec-
tricity discharges (a form of air ionization), although they can pose
severe explosion risks, occur during many industrial processes (e.g.,
paint spraying, bag filling, and surface coating). A monopolar
electrostatic precipitator is sufficient to generate ions of one po-
larity that bind to particulate matter. These particles are then
attracted by electrostatic forces to oppositely charged or grounded
collection plates. This process is commonly used in industrial clean
room, office, and home indoor air applications.
For proper management of air quality, air ionization techniques
are emerging as promising alternatives to conventional methods.
To date, air ionization techniques have been used extensively to
remove odors and VOCs from air flows, and their feasibility has
been demonstrated in sensitive manufacturing operations. The
future of air ionization will be brightened by continuing efforts to
improve their cost-effectiveness and minimize the production of
by-products. We anticipate that advances in nanotechnology,
biotechnology, and other related science sectors will result in air
ionization techniques with excellent performance for removing
VOCs and odorants from indoor air spaces.
Acknowledgements
This study was supported by a grant from the National Research
Foundation of Korea (NRF) funded by the Ministry of Education,
Science and Technology (MEST) (No. 2016R1E1A1A01940995). E. E.
Kwon also acknowledges the support of an NRF grant funded by the
Korean Government (MSIP) (No. 2014RA1A004893). This research
was also supported partially by the R&D Center for Green Patrol
 K.-H. Kim et al. / Environmental Pollution 225 (2017) 729e743
Technologies through the R&D for Global Top Environmental
Technologies funded by the Ministry of Environment (MOE), Re-
public of Korea.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.envpol.2017.03.026.
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