Plasma Remediation Technology For Environmental Protection: Changming Du Jianhua Yan

Advanced Topics in Science and Technology in China
ChangMing Du
JianHua Yan
Plasma Remediation
Technology for
Environmental
Protection
123
Advanced Topics in Science and Technology in
China
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ChangMing Du • JianHua Yan
Plasma Remediation
Technology
for Environmental Protection
123
ChangMing Du JianHua Yan
Sun Yat-Sen University Zhejiang University
Guangzhou, Guangdong Hangzhou, Zhejiang
China China
ISSN 1995-6819 ISSN 1995-6827 (electronic)

Advanced Topics in Science and Technology in China
ISBN 978-981-10-3655-2 ISBN 978-981-10-3656-9 (eBook)
DOI 10.1007/978-981-10-3656-9
Jointly published with Zhejiang University Press, Hangzhou
Library of Congress Control Number: 2017930407
© Zhejiang University Press, Hangzhou and Springer Natue Singapore Pte Ltd. 2017
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Preface
In the recent years, non-thermal plasmas, including glow discharge, corona discharge,
dielectric barrier discharge, gliding arc discharge, radio frequency discharge, and
microdischarge, have been continuously developed and utilized in few fields, such as
chemistry, biology, physics, biotechnology, medicine, and environmental science.
In Chap. 1 of this book, the types of non-thermal plasma, and the techniques of
plasma science for remediating contaminated soil, wastewater degradation, metal
recovery from waste solution, sterilization, and polluted air are described in detail. In
Chap. 2, development of non-thermal plasma fluidized bed (PFB) for remedi-ating
phenanthrene-contaminated soil, how 95% of phenanthrene can be removed with an
energy density of 5960 J/g soil %, and the proposal of possible mechanisms of the
phenanthrene degradation by the PFB are discussed. In Chap. 3, how a gliding arc
plasma reactor can be used for the degradation and discoloration of the textile dyes
solutions is explained. What type of kinetics is followed by the dis-coloration and
degradation for mixed dyes with zerovalent iron is also explained in the same chapter.
In Chap. 4, development of a microplasma jet system for reducing Cr(VI) in
wastewater and how 100% of Cr(VI) could be reduced after a 2-min discharge
treatment with an energy density of 300 J/mL water are elucidated. In Chap. 5, the
efficiency and effectiveness of surface sterilization using humid air gliding arc
discharge and how sterilization can be improved efficiently under dif-ferent air flow
rates and gap distances are described. In Chap. 6, development of non-thermal PFB for
decomposing volatile organic compounds is elaborated.
All research works were supported by the Natural Science Foundation of
GuangDong (2016A030313221), the GuangDong Public Welfare Research and
Capacity Building Project (2015A020215013), the Science and Technology New
Star in Zhu Jiang Guangzhou City (201312), and the National Natural Science
Foundation of China (50908237). The authors gratefully acknowledge the work of
DanYan Ma, ZhiYi Li, MuDan Xiao, and Jing Wang during their research.
Guangzhou, China ChangMing Du

Hangzhou, China JianHua Yan
v
About the Book
This book explains atmospheric plasma sterilization, air pollution control, solid waste,
and water treatment technologies. A novel non-thermal plasma fluidized bed was
developed for remediating phenanthrene-contaminated soil; 95% of the PHE was
removed with an energy density of 5960 J/g soil.%; and a possible mechanism of the
phenanthrene degradation by the plasma fluidized bed was also proposed. A gliding arc
plasma reactor was used for the degradation and discoloration of the textile dyes
solutions. The discoloration and degradation for mixed dyes with Fenton catalysis
follow pseudo-first-order kinetics. A microplasma jet system was developed for
reducing chromium (VI) in wastewater; 100% of Cr(VI) could be reduced after the 2-
min discharge treatment with an energy density of 300 J/mL water. Surface
sterilization using the humid air gliding arc discharge is rapid and effective. The
dynamic sterilization under different air flow rates and gap distances shows that
increasing air flow rates and shorter discharge gap distance could improve sterilization
efficiency. A novel non-thermal plasma fluidized bed was developed for cleaning air
and volatile organic compounds.
vii
Contents
1 Application of Plasma Technology for Remediating

Environment—An Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Plasma Generation and Application . . . . . . . . . . . . . . . . . . . . . . . . 1
1.3 Plasma Technology in Environmental Protection . . . . . . . . . . . . . . 2
References. . .............................................. 4
2 Remediation of Phenanthrene-Contaminated Soil
Using Non-thermal Plasma Fluidized Bed . . . . . . . . . . . . . . . . . . . . . . 7
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2.1 Experimental Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2.2 Materials and Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3 Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.1 Effect of the Solid Bed Location. . . . . . . . . . . . . . . . . . . . . 11
2.3.2 Effect of the Input Energy Density . . . . . . . . . . . . . . . . . . . 12
2.3.3 Effect of the Flow Rate of the Carrier Gas . . . . . . . . . . . . . 13
2.3.4 Effect of the Soil Moisture Content. . . . . . . . . . . . . . . . . . . 14
2.3.5 Role of Active Species . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.3.6 TOC Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3.7 Proposed Pathway of the PHE Degradation . . . . . . . . . . . . 17
2.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References. . .............................................. 19
3 Degradation and Discoloration of Textile Dyes Using
Gliding Arc Plasma Combined with Fenton Catalysis . . . . . . . . . . . . 21
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.2 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.2.1 Plasma Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.2.2 Materials and Analytical Methods . . . . . . . . . . . . . . . . . . . . 23
ix
x Contents
3.3 Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.3.1 Plasma Discoloration and Degradation of Single Dye . . . . . 24

3.3.2 Treatment Results of Mixed Dye Wastewater . . . . . . . . . . . 27
3.3.3 Discoloration and Degradation in the Presence
of Zerovalent Iron (ZVI) . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.3.4 Comparison of Different Research Studies
and Their Major Results . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4 Reduction and Removal of Cr(VI) from Aqueous Solution
by Microplasma. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 41
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 41
4.2 Experimental Details. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 43
4.2.1 Discharge Apparatus and Materials . . . . . . . . . . . . . . . . . .. 43
4.2.2 Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 44
4.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 44
4.3.1 Effect of Gas Flow Rate on Cr(VI) Reduction . . . . . . . . .. 44
4.3.2 Effect of Initial pH on Cr(VI) Reduction. . . . . . . . . . . . . .. 45
4.3.3 Effect of Stirring on Cr(VI) Reduction . . . . . . . . . . . . . . .. 46
4.3.4 Effect of Initial Cr(VI) Concentration on Cr(VI)
Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 46
4.3.5 Effect of Various Discharge Gas on Cr(VI) Reduction . . .. 46
4.3.6 Effect of Input Power on Cr(VI) Reduction . . . . . . . . . . .. 47
4.3.7 Effect of Ethanol on Cr(VI) Reduction and Removal . . . .. 48
4.3.8 Effect of Initial PH on the Removal of Cr(VI)
in the Presence of Ethanol . . . . . . . . . . . . . . . . . . . . . . . .. 49
4.3.9 Characterization of the Sediment. . . . . . . . . . . . . . . . . . . .. 50
4.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 52
4.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 56
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 57
5 Surface Sterilization by Atmospheric Pressure Non-thermal
Plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 61
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 61
5.2 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 62
5.3 Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 64
5.3.1 Destruction of Bacteria by Atmospheric Pressure
Non-Thermal Plasma. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.3.2 Influence of Air Flow Rate on the Sterilization
Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
5.3.3 Influence of Gap Distance Between Agar Surfaces
and Electrodes on the Sterilization Efficiency . . . . . . . . . . . 66
5.3.4 Temperature Variations of Surface Sterilization
Efficiency Under Different Contact Distances . . . . . . . . . . . 67
Contents xi
5.3.5 Influence of the Total Number of Bacteria

in the Surface on the Sterilization Efficiency. . . . . . . . . . . . 68
5.3.6 Scanning Electron Microscopic Photomicrographs
of E. Coli in the Treatment . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.3.7 Mechanism of Bacteria Inactivation by Non-thermal
Plasma. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
6 Removal of Volatile Organic Compounds Using Plasma
Fluidized Bed. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.2 Removal of Volatile Organic Compounds Using Plasma
Fluidized Bed with Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
6.2.1 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
6.2.2 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
6.3 Removal of Volatile Organic Compounds Using Plasma
Fluidized Bed with Activated Carbon. . . . . . . . . . . . . . . . . . . . . . . 78
6.3.1 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
6.3.2 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Reference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Chapter 1
Application of Plasma Technology
for Remediating Environment—An
Introduction
Abstract The non-thermal plasma-related classifications and the basic principles of

plasma treatment for environment protection are described in this chapter. This
chapter indicates some advanced application techniques of plasma technology,
such as gliding arc, for environmental protection and also puts forward the
potential ongoing developments of plasma technology.
Keywords Non-thermal plasma Plasma technology Pollution treatment

Environmental protection
1.1 Introduction
Nowadays, the methodologies being followed in the production and

manufacturing industries are based on large amounts of scientific knowledge
integrated with the advanced technologies of many subjects and are with
continuous innovative tech-niques. Plasma science, an emerging subject of the
fourth state of substance, has developed a totally new system of modern
technology and has derived many unique technologies coupled with the industrial
processes. The unique and innovative technologies of plasma science are now
deeply influencing the ways of modern industries and the ways of pollution
treatment for them as well. During the pollution abatement, “great difficulty in
degradation, resource recovery, and pollution control from source” are found to be
the international challenges, which have also become the focus of research.
1.2 Plasma Generation and Application
Plasmas are more or less ionized gases often referred to as the fourth state of matter.
They can be generated by a number of methods, such as combustion, flames,
electrically heated furnaces, electric discharges (glow discharge, corona discharge,
© Zhejiang University Press, Hangzhou and Springer Natue Singapore Pte Ltd. 2017 1
C. Du and J. Yan, Plasma Remediation Technology for Environmental Protection,
Advanced Topics in Science and Technology in China, DOI 10.1007/978-981-10-
3656-9_1
2 1 Application of Plasma Technology for Remediating …
dielectric barrier discharge, arc discharge, microwave discharge, and radio fre-
quency discharge), and shocks (electrically, magnetically, and chemically driven)
[1, 2]. Electric discharge plasmas are mostly used for laboratory and industrial
applications and are created by applying direct or alternating high voltage to a gas
or a gas mixture. This is generally referred to as gas discharge plasmas.
Depending on the energy level, the gas discharge plasmas can also be classified
into two categories: thermal and non-thermal plasmas [2, 3]. In thermal plasmas,
the tem-peratures of the plasma components approach thermal equilibrium, which
is why these plasmas are often referred to as equilibrium plasmas. On the other
hand, in non-thermal plasmas, also referred to as non-equilibrium plasmas, the
temperatures of the plasma components are not the same and electrons often have
much greater temperatures than the other gas components. Thermal plasmas are
generated in conventional electric arcs or plasma torches. Non-thermal plasmas
are generated in conventional glow discharge, dielectric barrier discharge, corona
discharge, gliding arc discharge, and microdischarge [1–5].
1.3 Plasma Technology in Environmental Protection
To find out the ignition methods of plasma that combine the advantages of both
thermal plasma (high energy density) and non-thermal plasma (high electron
temperature but low background temperature) is one of the significant challenges
for the current plasma technologies. In other words, initiating non-thermal plasmas
under atmospheric conditions provides many advantages, such as high energy
density, high efficiency, easy operation, and low costs, as no vacuum equipment is
needed, which is beneficial to the breakthrough for the large-scale applications of
cold plasmas for industrial and environment-friendly energy purposes.
In the beginning of the 20th century, the gliding arc discharge was first used for
the purpose of nitrogen-based fertilizer production in chemical applications [6]. In
1994, Czernichowski had demonstrated some successful applications of the
gliding arc in laboratory and industrial chemical processes [4]. Since 2003, some
gliding arc reactors patented in China have been developed in our laboratory with
the aim of application for energy- and engineering-friendly environment [7–13].
Typical gliding arc discharges are produced between at least two electrodes and
across the fast gas flow. As shown in Fig. 1.1, gliding arc discharge yields a
typical non-thermal plasma that develops between at least two electrodes placed
in a flat and fast gas flow. When the high-voltage DC or AC power source
provides high enough voltage between the electrodes, the gas flow in the gap
between the elec-trodes is broken down to form the arc. The arc is then pushed
downstream by the gas flow and glides along the electrode surface until it
quenches. After the decay of discharge, there is a new breakdown at the narrowest
gap and the cycle is repeated. This periodical discharge evolves from an arc to a
discharge, containing both quasi-equilibrium and non-equilibrium phases [4]. The
main advantages of the gliding arc discharges are as follows [4]:
1.3 Plasma Technology in Environmental Protection 3
Fig. 1.1 Schematic

representation of start,
life, and disappearance of
the gliding arc discharges
(i) The gliding arc discharges perform their own maintenance on the
electrodes, preventing chemical corrosion and erosion.
(ii) The electrodes do not need to be cooled; the electric energy is directly and
totally transferred to the processed gas.
(iii) Multielectrode systems can be installed easily in large gas lines.
(iv) Any gas or vapor, including polluted air, can be directly processed.
Moisture droplets, mists, and powders can be present. A gas of any initial
temperature and pressure can be accepted.
Initially, the 2D flat geometry of the gliding arc discharge was developed in
many chemical processes, but later, many applications preferred 3D cylindrical
geometry. Based on the 2D or 3D geometry, some gliding arc reactors with new
structures, such as rotating gliding arc, vortex gliding arc discharge, and gas–
liquid gliding arc discharge, were also designed and developed [14–16]. Two or
more electrodes (three phases; n phases; and parallel, serial, or mixed mounting)
for gliding arc reactors can be developed for an industrial size plant with DC or
AC power [4].
Based on the special construction of gliding arc, gliding arc plasma reactors can
directly process different gases (air, water vapor, gas–liquid mixture, Ar, O2, N2,
H2S, CO, CO2, hydrocarbons, and their mixtures) at a negligible pressure drop.
Many applications, mostly for energy engineering and environment control, were
successfully developed in laboratory and industrial scale reactors [4, 7–17]:
• Emission control of industrial volatile organic compounds (toluene, xylene,
heptane, and tetrachloroethylene), NH3, phenols, formaldehyde, organic
nitrates, diluted H2S or mercaptans, etc.;
• Emission control of soot, polyaromatic hydrocarbons, SOx, and NOx;
• Complete or partial incineration of concentrated H2S or H2S + CO2 mixtures;
• Conversion of natural gas into syngas (H2 + CO);
• Reforming of heavy petroleum residues;
• Decomposition and incineration of concentrated Freons;
• CO2 dissociation;
• Overheating of steam, oxygen, and other gases or flames;
• Ignition of propellants;
• UV generation;
• Decontamination of soil or industrial sands;
4 1 Application of Plasma Technology for Remediating …
• Organic wastewater treatment;

• Activation of organic fibers or activated carbon; and
• Sterilization.
Inexpensive gliding arc discharges can considerably reduce the energy con-
sumption of existing industrial processes relating to volatile organic compounds
(VOCs) and sulfur-containing compounds. Up to 75–80% of the electrical energy
can be dissipated in the non-equilibrium zone of the gliding arc discharge. It is
clear that this continuous, powerful, and atmospheric pressure discharge could be
applied for energy engineering and environment control reactions with high
efficiency and selectivity.
References
1. Bogaerts A, Neyts E, Gijbels R, van der Mullen JJAM. Gas discharge plasmas and their
applications. Spectrochim Acta B. 2002;57(4):609–58.
2. Petitpasa G, Rolliera JD, Darmonb A, Gonzalez-Aguilara J, Metkemeijera R, Fulcheria L. A
comparative study of non-thermal plasma assisted reforming technologies. Int J Hydrogen
Energ. 2007;32(14):2848–67.
3. Tendero C, Tixier C, Tristant P, Desmaison J, Leprince P. Atmospheric pressure plasmas: a
review. Spectrochim Acta B. 2006;61(1):2–30.
4. Czernichowski A. Gliding arc applications to engineering and environment control. Pure
Appl Chem. 1994;66(6):1301–10.
5. Fridman A, Nester S, Kennedy LA, Saveliev A, Ozlem MY. Gliding arc gas discharge. Prog
Energ Combust. 1998;25(2):211–31.
6. Naville AA, Guye CE, Guye P. Gas reactions at the temperature of the electric arc, French.
Patent FR361827. 1905
7. Yan JH, Chi Y, Li XD, Jiang XG, Ma ZY, Wang F, Jin YQ, Du CM, Ni MJ, Cen KF. Gliding
arc discharge plasma device for organic waste water treatment, China. Patent CN1557731A.
2004.
8. Yan JH, Li XD, Chi Y, Ma ZY, Du CM, Bo Z, Cen KF. A volatile organic compounds gas
treatment device, China. Patent CN2817959Y. 2005.
9. Du CM. A rotary gliding arc discharge plasma device for volatile organic compounds gas
treatment, China. Patent CN201131940Y. 2007
10. Du CM. A three phase gliding arc non equilibrium plasma device for water treatment, China.
Patent CN201099636Y. 2007.
11. Du CM. Non equilibrium plasma generating apparatus for spray disinfection sanitizer,
China. Patent CN101156955B. 2010.
12. Du CM. Non equilibrium plasma device for removing volatile organic compounds and
generating hydrogen, China. Patent CN101279715 B. 2011.
13. Du CM, Yan JH, Cheron B. Decomposition of toluene in a gliding arc discharge plasma
reactor. Plasma Sources Sci T. 2007;16:791–7.
14. Lu SY, Sun XM, Li XD, Yan JH, Du CM. Decomposition of toluene in a rotating glidarc
discharge reactor. IEEE T Plasma Sci. 2012;40(9):2151–6.
References 5
15. Ren Y, Li XD, Yu L, Cheng K, Yan JH, Du CM. Degradation of PCDD–Fs in fly ash by
vortex-shaped gliding arc plasma. Plasma Chem Plasma P. 2013;33:293–05.
16. Du CM, Shi TH, Sun YW, Zhuang XF. Decolorization of acid orange 7 solution by gas–
liquid gliding arc discharge plasma. J Hazard Mater. 2008;154(1–3):1192–7.
17. Du CM, Liu H, Xiao MD, Gao D, Huang DW, Li ZY, Chen TF, Mo JM, Wang K, Zhang
CR. Adsorption of iron and lead ions from an aqueous solution by plasma-modi fied
activated carbon. Ind Eng Chem Res. 2012;51(48):15618–25.
Chapter 2
Remediation of Phenanthrene-
Contaminated Soil Using Non-thermal
Plasma Fluidized Bed
Abstract A non-thermal plasma fluidized bed (PFB) was developed for remediat-
ing phenanthrene (PHE)-contaminated soil. After a 25-min treatment, 95% of the
PHE was removed with an energy density of 5960 J/g soil, air flow rate of 20
L/min, and soil moisture of 10%. The effects of the solid bed location, energy
density, the flow rate, and the carrier gas were explored. It was found that
decreasing the distance between the solid bed and electrodes properly and
increasing the input energy density were favorable for PHE degradation. There
existed appropriate flow rate and soil moisture for a higher efficiency. By means of
various methods, the roles of the active species on the degradation efficiency and
the products formed during dis-charge were analyzed. Possible mechanism of the
PHE degradation by the PFB was proposed. Furthermore, a brief comparison with
other competitive processes was performed, indicating that the proposed PFB was
a promising alternative process for remediating PHE-contaminated soil [1].
Keywords Plasma Fluidized bed Contaminated soil Phenanthrene Remediation
2.1 Introduction
Due to the rapid advancements in the chemical industry, various persistent organic
pollutants, such as chlorinated organics, polycyclic aromatic hydrocarbons
(PAHs), and p-nitrophenol, have been extensively developed and accumulated in
the industry sites. For instance, the concentration of the leftover PAHs in many
coking industry lands in China exceeded 100 mg/kg [1]. The sites are
contaminated by persistent organic pollutants (POPs) of high potential toxicity,
mutagenicity, and carcinogenicity are posing greater threats to ecology,
environment, and human health [2]. On the other hand, many contaminated sites
still have economic value for reuse as commercial or residential areas. Therefore,
remediating the soil con-taminated by POPs is an essential task.
Various technologies, such as bioremediation [3], electrodynamic remediation
[2], chemical remediation [4], solvent extraction [5], and thermal treatment [6],
3656-9_2
8 2 Remediation of Phenanthrene-Contaminated Soil Using …
have been proposed for remediating the soil contaminated by POPs. However,
these traditional methods may not meet the demand of rapid utilization due to the
long treatment period, the secondary pollution, or adding chemicals. Since the last
decades, advanced oxidation progresses (AOPs), such as photochemical method
[7], and Fenton progress [8] have drawn remarkable attention for remediating the
soil contaminated by POPs. As one of the newly developed AOPs, non-thermal
plasma is also increasing the awareness of the soil remediation for high efficiency
and economic advantages. In the recent years, several studies were conducted to
prove that a pulsed corona discharge plasma is capable of removing the pen-
tachlorophenol and p-nitrophenol pollutants from the soil [9–12].
To date, however, there is still no report on remediating the soils contaminated by
the persistent organic pollutants using the gliding arc process, a promising plasma
technique. Previous studies indicated that gliding arc discharge process is very
effective at many chemical processes, such as abatement of volatile organic
compounds (VOCs), methane reformation, and water purification [13–16].
Furthermore, the gliding arc discharge has greater potential in an aspect of the scaling
up of the application due its simple equipment, flexible and controllable operations,
high non-equilibrium state, and high efficiency in organic pollutants removal [17]. The
non-thermal plasma fluidized bed (PFB) combining gliding arc plasma and fluidized
bed is the most notable proposal. The ideal PFB gives a lot of opportunities for varied
heterogeneous processes, such as material process [18], fuel reformation [19], and
plasma-catalyst reaction [20] due to excellent heat transfer and mass transfer inside a
plasma reactor, and other original features, such as the microdischarge between the
solid particles. It is believed that gliding arc discharge in a fluidized bed can be an
alternative for remediating the soil polluted by organics.
The aim of this chapter is to investigate the potential for soil remediation
through PFB. The gliding arc plasma presented in a previous study was chosen as
plasma source [14]. The solid bed was separated from the discharge zone with a
rotating parabolic structure to further improve the contact between discharge gas
and solids, which is different from the former GAD fluidized bed that lack
uniformity, dead zone, and particle attrition. PHE, a typical PAH, was used as the
model pollutant. In this chapter, the performance of this novel PFB considering
the input energy density, air flow rate, and soil moisture was evaluated. By means
of various analysis methods, the degradation procedure was investigated and
discussed. A possible pathway was proposed based on the experimental result.
2.2 Experimental Section
2.2.1 Experimental Setup
The schematic representation of the experimental setup for remediating PAH-

contaminated soil is shown in Fig. 2.1. The system mainly consists of four parts:
(1) the power supply, (2) the gas source, (3) the plasma reactor, and (4) an
2.2 Experimental Section 9
Fig. 2.1 Schematic diagram of the experimental setup
analysis section. The plasma reactor was connected to a high-voltage AC power

supply with a neon transformer ranging from 7.5 to 15 kV. An oscilloscope with a
high-voltage probe (Tektronnix P6035) and a current probe (Tektronnix TP301A)
is used to measure the curves of discharge, and the input energy could be simulta-
neously calculated.
The plasma reactor was made up of a cylindrical quartz glass (U = 100 mm, H
= 200 mm). Two knife-shaped stainless steel electrodes were placed symmetri-
cally on the opposite sides of the reactor. Above the electrodes was a stainless grid
(300 mesh), which works as the solid bed supporter, and the soil samples were
placed on the solid bed during the discharge. To prevent soil particles from
escaping away with the carrier gas, a dust trap was also installed.
When applying a high voltage, the gas passing between the electrodes was
broken down by the strong electric field, igniting the cycle of the gliding arc.
Then, the length of the arc increased and moved with the gas flow until cooling
down, and the new arc was generated. Carrier gas with active species (such as
high energy electron, different radicals, and excited species) fluidized the soil
particles and reacted with PHE in soil. The exhausted gas was directed through
hexane to gather the intermediates and the residual PHE.
2.2.2 Materials and Analyses
Phenanthrene and other standards used were purchased from Sigma-Aldrich

(Shanghai, China). Methanol with chromatographic purity was supplied by
Honeywell (America). All other reagents were of analytical grade without any
further purification.
The soil sample was prepared artificially. Clean soil was collected from the
campus of Sun Yat-sen University in Guangzhou, China. The contaminated soil
samples were prepared artificially. The features of the clean soil were as follows:
the contents of sand, silt, clay, and organic matters were 3.0, 70.7, 26.3, and
5.44%, respectively; pH value is 6.6; and loss on ignition was 5.8%. To avoid the
organic influence, the soil samples were extracted with methanol in ultrasonic bath
repeatedly for five times.
The soil was polluted with PHE in the mixture solution (dichloromethane/
acetone) with a ratio of 1:1 (v/v). The concentration was 200 mg/kg after the
evaporation of solvent was completed.
The 15-g contaminated soil was treated every time. Prior to the treatment, the
humidity of the soil was adjusted to 10%.
At the given intervals, 1 g of treated soil sample from the mixed-well solid bed
(as the fly ashes were almost trapped in the solid bed by its filter) was extracted
with 10 mL of methanol in ultrasonic bath repeatedly for three times. All the
extracts were mixed and dehydrated by Na 2SO4 before concentrated by rotary
evaporation. Finally, the extracts were dried up by soft pure nitrogen of 99.99%
purity, and the volume was re-set to 1 mL with methanol. The pre-treatment of the
hexane solution was the same as the extracts.
Prior to detection, the solution was filtered through a 0.22-lm nylon filter.
Quantification of PHE was performed with a high-performance liquid chromatog-
raphy with a variable wavelength detector set at 254 nm (HPLC, Shimadzu,
Japan). An 85:15 (v/v) mixture of methanol:water was employed as mobile phase
with a flow rate of 1.0 mL/min.
The PHE efficiency (ηPHE) can be calculated as follows:
Þ
g ¼ ðc0 cÞm mG 100% 2:1
PHE
c0m ð
where c0 and c represent the initial concentrations of the PHE in soil sample and
treated soil, respectively, while m and mG represent the mass of the treated soil
and the mass of PHE absorbed in hexane, respectively. However, the mass of PHE
absorbed in hexane was negligible, which is detailed in the following section.
Therefore, the PHE degradation efficiency can be simplified as follows:
Þ
g ¼ ðc0 cÞ 100% 2:2
PHE
c0 ð
The mineralization of PHE was measured by a total organic carbon analyzer

(TOC; Shimadzu, Japan). Gas chromatography–mass spectrometry (GC–MS;
Agilent Co., U.S.) was employed to identify the intermediates in the soil and
exhausted gas. In the GC system, the GC column was a capillary column of 30 m
long and 0.32 mm diameter. The temperature program was first set at 35 °C and
heated up to 120 °C with a heating rate of 15 °C/min, held at 120 °C for 1 min
followed by heating up to 260 °C with a heating rate of 4 °C/min, and held at a
final temperature of 260 °C for 10 min.
The exhaust-gas ozone concentration is measured by the indigo dye reaction.

Hydrogen peroxide is measured by a Hydrogen Peroxide ET8600 m.
The energy density is defined as follows:
Þ
ED ¼ P T 2:3
m ð
where P is the power of plasma discharge (calculated by the voltage and discharge
current measured by an oscilloscope) and, in this study, different input powers
were offered by changing the voltage supplied. T is the treatment time (s), and m
is the mass of soil treated (g).
The energy efficiency of the PFB system was defined as follows:
Þ
G ¼ c0 c 2:4
ED ð
2.3 Results and Discussions
2.3.1 Effect of the Solid Bed Location
The potential of the PFB for PHE removal from the soil and the effect of the solid bed
location, i.e., the distance between the bottom of the solid bed and the neck of the
electrodes, were investigated first. Distances such as 140, 145, 150, 155, and 160 mm
were taken into account. Air was used as carrier gas with a flow rate of 15 L/min. As
shown in Fig. 2.2, the PFB performed very well in remediating the PHE-contaminated
soil. To illustrate, after a 25-min treatment, the PHE degradation efficiency was up to
87.31% and the residual concentration was 25.36 mg/kg, while
Fig. 2.2 Effect of location of 100

the solid bed on the PHE distance=160 mm
PHE degradation efficiency(%)
distance=155 mm
degradation (energy density =
80 distance=150 mm
3466 J/g soil, air distance=145 mm
flow rate = 20 L/min, and soil distance=140 mm
moisture = 10%) 60
40
20
0
0 5 10 15 20 25
Treatment time (min)
the Chinese environmental standard claims that the highest residual concentration
of PHE for commercial and industrious reuse is 30 and 50 mg/kg, respectively
[21], which confirmed that the proposed system had the potential for remediating
the soil in such a shorter treatment period.
In Fig. 2.2, it can also be found that the distance was the smallest and the PHE
degradation efficiency was the highest. This could be ascribed to the discharge
characteristics between electrodes. When connected to a high voltage, energetic
electrons were produced and then the ionization, excitation, and dissociation of the
carrier gas were ignited to generate highly active radicals and molecules (such as
OH, O3, and H2O2), which might be responsible for the PHE degradation.
However, the lifetime was very short for most of the active species produced, such
as OH and O, leading to the inactivation of these species even before they work if
the distance between the solid bed and the neck of electrodes is too large.
Furthermore, there would also be discharge between the stainless solid bed and
each electrode if they were close enough. Hence, a proper location might allow the
full utilization of the short-lifetime active species together with a better transfor-
mation between the soil particle and the active species, whose lifetime was very
short. Therefore, in the following experiment, the distance of 140 mm was chosen.
2.3.2 Effect of the Input Energy Density
Input energy density can characterize the energy demand of the proposed system for
treating the contaminated soil, which is a very important parameter for the operation of
plasma system. Hence, the energy density as function of the PHE degradation
efficiency as well as the energy efficiency has been studied, as illustrated in Fig. 2.3. It
can be seen that PHE degradation efficiency is partially depended on the energy
density. When the energy density was set as 3973 J/g soil, about 94.1% of PHE was
removed, while approximately 37.4, 48.7, 71.1, and 84.65% of PHE were degraded
with an energy density of 1306, 1986, 2800, and 3466 J/g soil within the same time,
Fig. 2.3 Effect of the energy 6.0x10-5

100
PHE degradation efficiency (%)
density on the PHE

degradation efficiency and
5.6x10-5
Energy density (mg/J)
the energy efficiency (air flow 80

rate = 20 L/min and soil
5.2x10-5
moisture = 10%) 60
40 4.8x10-5
20
4.4x10-5
4.0x10-5
0
1500 2000 2500 3000 3500 4000
Energy density (J/g soil)

2.3 Results and Discussions 13
respectively. A higher energy density in the same time span means more energy input
in the system, where a more number of available electrons initiate the reaction
opportunities simultaneously. It is generally believed that more energetic electrons are
produced with higher input energy, thus leading to the accelerated formation of active
species, such as ozone, H2O2, and OH [22]. These active species play important roles
in PHE degradation, thus resulting in its enhancement. On the other hand, when the
energy density was continuously increasing, the discharge was significantly more
intense because of which more plasma channels and microdis-charges occurred
between the electrodes and the solid bed. In this way, the PHE-contaminated soil
particle would directly collide with the energetic electrons and degrade rapidly, further
increasing the performance.
Although being different from the degradation efficiency, energy efficiency of
this PFB first decreased slightly as the input power increased, as shown in Fig. 2.3.
Although more energy could produce more active species resulting in the
enhancement of the degradation, during this procedure, more active species were
inactivated before contacting with pollutants. Furthermore, some part of energy in
discharge was not utilized and was consumed in other aspects. For instance, the
more intense luminescence was the consumption of the energy.
2.3.3 Effect of the Flow Rate of the Carrier Gas
In a PFB system, the gas flow rate plays an important role. The fluidized bed
requires proper velocity for better heat transfer and mass transfer. As for the
gliding arc plasma, it also requires a reasonable velocity for gliding. Therefore, the
PFB performance was investigated in function of air flow rate. Control experiment
of PHE in soil was only performed by aeration, as illustrated in Fig. 2.4.
Surprisingly, although the aeration did result in a small fraction of PHE entrained
in the air flow, the residual PHE in air flow was negligible within 25-min discharge
treatment. This denoted that PHE in air flow could also be degraded and that the
PHE degradation by plasma be accounted for the PHE removal.
Figure 2.5 indicates that the flow rate of carrier gas has significant influence on the
degradation performance. The increase in the gas flow rate was followed by the
increase in the PHE degradation efficiency. This is due to a fast flow rate that was
favorable for the gliding of the discharge arc, so the discharge zone was forced
upstream to a larger area. In this way, more PHE-contaminated soil was immersed in a
reactive zone. Meanwhile, since soil has a strong adsorption for the PHE, des-orption
of the PHE was very difficult; in order to remove the PHE strongly sorbed from the
soil particle, better mass transfer is required. A higher flow rate improves the mass
transfer between discharge and solid phases, so that PHE in the particles was more
likely to react with the active species generated in discharge. However, the further
increase in flow velocity may shorten the resident time of active species in the fluidized
bed, which is not beneficial for fully utilizing the plasma species. Therefore, the
optimal flow velocity chosen in this experiment was 20 L/min.
Fig. 2.4 Effect of air flow on
PHEdegradationefficiency(%)
100 3.5x10-5
the PHE removal (energy 80 3.0x10-5
density = 3973 J/g soil and
encyEnergy
(mg/J)effici
0.0
soil moisture = 10%) 2.5x10-5
60 2.0x10-5
40 1.5x10-5
1.0x10-5
20 5.0x10-6
5 10 15 20 25 30
Flow rate (L/min)
100 flow rate=5 L/min
Fig. 2.5 Effect of the flow

rate on the PHE degradation
efficiency(%)
flow rate=10 L/min

and the energy efficiency
80 flow rate=15 L/min
(energy density = 3973 J/g flow rate=20 L/min
soil and soil moisture = 10%) flow rate=25 L/min
PHE degradation
60
40
20
0 5 10 15 20 25
In addition, a similar energy variation of efficiency as function of the flow rate

was obtained, which may be ascribed to the facts that the excellent mass transform
enhanced the utilization of the active species and, in turn, the input power was
fully used. With a too large flow rate, the short residence time was not beneficial
for the interaction and reaction.
2.3.4 Effect of the Soil Moisture Content
Soil moisture content is one of the most important factors to consider in soil treatment.
The experiments of PHE degradation in soil were conducted with various moisture
contents. The results of the experiments are illustrated in Fig. 2.6. It was obvious that
soil moisture was beneficial for PHE degradation in the proposed system. In dry soil,
about 70.8% of PHE was degraded within 25 min of discharge treatment and PHE
efficiency was up to 95.2% with the soil moisture content of
Fig. 2.6 Effect of soil 100

moisture content on the PHE
efficiency(%)
moisture =0%
degradation (energy density 80 moisture =5%
moisture =10%
= 3973 J/g soil and air flow moisture =15%
rate = 20 L/min)
PHE degradation
60
40
20
0 5 10 15 20 25
10% within the same discharge time; however, PNP degradation efficiency
decreased up to 77.8% when the soil moisture continued to increase up to 15%. In
air plasma, oxygen molecules could collide with energetic electrons generated in
the discharge and then series of reactions took place. By these reactions,
+
numerous active species, such as O 2 , O, and O3, were produced. Both energetic
electrons and the produced oxygen-derived species could attack the H2O
molecules, thus leading to the following reactions [22, 23]:
H2O þ e ! H þ OH þ e ð2:5Þ
H þ O2 ! HO2 ð2:6Þ
O þ H2O ! H2O2 ð2:7Þ
O þ H2O ! 2OH ð2:8Þ
OH þ OH ! H2O2 ð2:9Þ
Water content in soil could be evaporated into air with the dual role of the
thermal effect of discharge together with the air flow to participate in the above-
mentioned reactions. In addition, high-energy electrons could also react with
water molecules in moist soil to form OH radicals and H 2O2, which have stronger
oxi-dation potential than the oxygen-derived species. Therefore, higher PHE
degrada-tion efficiency in moist soil (moisture content, 10%) could be achieved,
when compared with that in dry soil, implying that OH radical might work in PHE
degradation.
Further increase in moisture content was hindered, which was unfavorable for
PHE degradation, as it leads to the coalescence of soil particles and the mass
transfer between discharge gas and soil particles.
2.3.5 Role of Active Species
To investigate the effect of various active species on the PHE degradation in soil,
reactive species, such as H2O2 and O3, formed by the discharge were determined
in the outlet gas. It was found that the concentrations of O 3 and H2O2 in the
exhausted gas with clean soil were higher than that in polluted soil for both the
reactive species. CH2O2 and CO3 were up to 7.6 and 0.3 mg/L, respectively, with
clean soil, while in polluted soil, CH 2O2 and CO3 were decreased up to 3.7 and
0.11 mg/L, respectively. The experimental results indicated that both H2O2 and O3
play a significant role in the PHE degradation.
The role of OH radical was also studied by adding ethanol, an effective OH
radical scavenger [24]. Different volumes of ethanol solutions were added to soil
samples, as depicted in Fig. 2.7.
Obviously, the addition of radical scavenger could significantly influence PHE
degradation. When ethanol was added, the reduction rate decreased rapidly and,
with an increase in the amount of ethanol, the PHE degradation efficiency
decreased. The experimental results indicated that OH radical played a very
important role in PHE degradation and the decrease in OH radical could directly
inhibit PHE degradation.
* +
Furthermore, a previous study also demonstrated that N 2 and N2 generated in
air plasma area can directly react with PAHs in gas and that energetic electrons
can dissociate the C–H bonds of targets for further degradation [25].
Therefore, it is possible to clear that the reactions between PHE, oxygen-
derived radicals, nitrogen-derived radicals, and electrons have an impact on PHE
degradation.
Fig. 2.7 Effect of adding OH 100

radical scavenger to PHE 2 mL ethanol
PHE degradation efficiency(%)
degradation (energy density = 1 mL ethanol

3973 J/g soil, air
flow rate = 20 L/min, and soil 80 no additive
moisture = 10%)
60
40
20
0
0 5 10 15 20 25

2.3.6 TOC Analysis
Changes in the TOC value of the soil sample directly reflect the mineralization of
PHE in the system. Figure 2.8 shows the TOC removal rate of the soil during the
discharge. The decreased TOC value accompanies the discharge time in 40 min. It
means that a fast and complete mineralization occurs under the plasma conditions.
According to Fig. 2.8, in the first 10 min, the TOC removal occurred slowly and
then accelerated gradually, indicating that the PHE oxidation could be divided into
two stages. The PHE was first degraded into smaller organics and then
mineralized to CO2 or other gas products.
2.3.7 Proposed Pathway of the PHE Degradation
To further identify the products, GC–MS was employed. Less hazardous compound
intermediates such as 9,10-phenanthrenequinone that has been detected as one of the
main products in photodegradation process [26] were detected in Table 2.1.
Of note, trace product of NO2 substituent was detected in exhausted gas, indi-
cating that NOX emitted by the nitrogen and oxygen discharge could also react
with PHE or the unstable intermediates. However, the abovementioned
intermediates represent only the portion of reaction intermediates, since some
intermediates were trace products and could not be detected in the current GC–MS
analysis. The degradation pathways are tentatively proposed in Fig. 2.9.
As shown in Fig. 2.9, the oxidation process was probably initiated by the attack of
oxidizing species at positions 9 and 10 of the PHE to yield the theoretical product
9,10-phenanthrenequinone. Intermediate 9,10-phenanthrenequinone could be
Fig. 2.8 TOC removal 70

efficiency as function of
treatment time 60
TOC removal efficiency (%)
50
40
30
20
10
0 10 20 30 40
Table 2.1 Compounds identified in the products
Products
Exhausted gas
Treated soil
1 14
13
+
4 2 12 OH,O ,O 3 HO etc
5 3 2 2 2
11
6 8 10
7 9
OH
O
OH
OH
+ O CHO
samaller organcis or CO2
O CHO
OH
Fig. 2.9 Possible pathway of the degradation of phenanthrene by the PFB
cleaved and could yield phthalate acid [27]. After further cleavage over the rest
benzene ring, various substances, such as esters, alkanoic acid, alkanol, and
alkane, were yielded [28]. Given sufficient reaction time, all the intermediates
could be completely mineralized.
A brief comparison of the PFB process with other technologies utilized for
PHE degradation has been summarized in Table 2.2. It is observed that the ozone
treatment showed great potential for PHE degradation due to a higher efficiency
and a shorter period over other processes. However, the proposed PFB process
was comparable to the previous ozone treatment, and this newly developed
process showed higher efficiency in seriously polluted soil abatement. Hence, it is
believed that PFB process is an alternative and efficient method to degrade PHE
in soil, especially for those polluted sites that require quick remediation.
2.4 Conclusions 19
Table 2.2 Comparison between PFB process and other competitive technologies for remediating
PHE-contaminated soil
Method C0 (mg/kg) Period Capacity (g) Degradation References
efficiency (%)
Bioremediation 200 28 day – 100 [3]
Photodegradation/Fe 100 8h 10 100 [7]
(III)
Ultrasound/soil 101.04 30 min 10 70 [29]
washing
Ozone treatment 10 20 min 10 90 [30]
PFB process 200 25 min 15 95 This study
2.4 Conclusions
In the present study, the remediation of PHE-contaminated soil by a novel plasma

fluidized bed was investigated. The results showed that PHE in soil could effec-
tively degrade after the discharge treatment. This new system promises high effi-
ciency, for efficiency up to 95% could be attained in 25 min under the optimal
conditions. The proposed reactor also has economic advantage compared with
other remediation technologies with a much shorter treatment period without any
other additional chemicals, except for energy input. Therefore, the plasma
fluidized bed is a promising alternative technique for remediating the organics-
polluted soil, espe-cially for heavily polluted soil, to reuse.
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Chapter 3
Degradation and Discoloration of Textile
Dyes Using Gliding Arc Plasma Combined
with Fenton Catalysis
Abstract Degradation and discoloration of three kinds of representative textile dyes

[Alphazurine A, Acid Orange II (AOII), and Acid Anthraquinone Blue (AAB)] and
their mixture were investigated using the gliding arc discharge plasma, which pro-
duces reactive species, such as OH, NO, and H 2O2, and other excited state molecules
formed in the discharge and induces strong oxidizing effects on the target solution. The
influence of zerovalent iron (ZVI) as Fenton catalysis on the efficiency of treatment
was also studied. The acidic environment created by gliding arc discharge (GAD) is
the cause of ZVI to release ferrous ions that act as a catalyst for decom-posing
hydrogen peroxide emitted by GAD. We treated the dyes with the UV-Vis analyses and
chemical oxygen demand (COD) measurements to confirm the dis-coloration and
degradation of the dyes, respectively. It has been observed that the discoloration ratios
are almost complete (i.e., 96.55% for AA, 94.66% for AOII, and 89.69% for AAB).
The discoloration and degradation for mixed dyes with ZVI follow pseudo-first-order
−1
kinetics. The kinetic constants of bleaching are 0.0301 and 0.0385 min at 483 and
−1
637 nm, respectively, and of degradation is 0.0101 min , which is much higher than
−1
0.0019 min , the kinetic of mixed dyes without ZVI. The degradation efficiency for
the mixed solution with an addition of ZVI turns out to be 44.18% higher than that
without. All these abovementioned points mean that GAD combined with ZVI can be a
promising technology in the area of textile dye wastewater treatment (Li in Study on
the treatment of dye wastewater in a gliding arc discharge plasma reactor. Yat-sen
University, 2013, [1]).
Keywords Gliding arc discharge Plasma Dyes wastewater Degradation

Discoloration Fenton catalysis
3.1 Introduction
The large quantity of wastewater produced by textile industry is characterized by

strong color, high chemical oxygen demand (COD), and biotoxicity. The dye
wastewater exhibits serious consequences to human health and potential pollution
3656-9_3
22 3 Degradation and Discoloration of Textile Dyes Using Gliding Arc …
to the environment [2]. Currently, the conventional treatments, such as biodegra-

dation and flocculation, used by the textile manufactures become inadequate due
to a high number of benzene cycles [3].
In order to solve this problem, research studies have been conducted to find
some more efficient approaches, such as Fenton reaction, photo catalysis, and non-
thermal plasma, for the degradation and discoloration of textile dye wastewater
[4–6]. These approaches all belong to advanced oxidation processes (AOPs) that
generate hydroxyl radicals (OH) during the treatment [7, 8]. Among these, non-
thermal plasma is especially efficient for producing active species to treat the dye
wastewater. Gao et al. [9] investigated the contact glow discharge electrolysis
(CGDE) of two dyes under different concentrations, temperature, and mediums.
Sun et al. [10] chose gas-liquid pulsed discharge plasma reactor and conducted
treatments on Methyl Orange dye wastewater. Garcia-Segura et al. [11]
synthesized TiO2 photoanode by atmospheric plasma spray and achieved a solar
photoelec-trocatalytic degradation of azo dye. Gliding arc discharge (GAD) has
also been found suitable for degrading dyes. GAD is actually a quenched plasma
operated at atmospheric pressure [12], and it is generated with at least two
electrodes in a fast gas flow. There is an increasing application in energy and
environmental fields, such as hydrogen production, degradation of organic
wastewater, and modification of materials [13, 14]. Doubla et al. [15] used gliding
electric discharge at atmo-sphere to decolorize Bromothymol Blue. Abdelmalek et
al. [16] reported the degradation effects of gliding arc on the dyes orange II and
malachite green. Du CM et al. compared the influence of degradation for different
forms of TiO2 as catalysts on the gliding arc treatment of Acid Orange II [17, 18].
The gliding arc plasma can degrade complex pollutants without any complicated or
expensive chemicals and catalysts additionally. Therefore, in this chapter, the
discoloration and degradation of three kinds of representative textile dyes (triph-
enylmethane dye, Alphazurine A; azo dye, Orange G; and anthraquinone dye, Acid
Anthraquinone Blue) are investigated using the gliding arc. It is also focused on the
influence of zerovalent iron (ZVI) that acts as a catalyst in the treatment process.
3.2.1 Plasma Apparatus
The apparatus used in the treatments is shown in Fig. 3.1. The gliding arc treatment
device is made up of a reactor with an alternate current high-voltage power supply
(220 V/10 kV, 50 Hz). The reactor, being the main part of the plasma device, has a
water-cooled glass vessel (1 L), two knife-shaped electrodes (made from stainless steel
of 95 mm long, 35 mm wide, and 4 mm thick), and a Teflon cover. The feeding gas
and dye solution are supplied separately by an air pump and a water pump and then are
mixed and atomized by the spray nozzle (diameter, 0.99 mm) mounted in the Teflon
cover. When the treatment device is electrified by the
Fig. 3.1 Schematic

representation of the gliding
arc discharge plasma device
high-voltage power supply, gliding arc is generated between the electrodes, which
is called plasma zone. At the same time, the atomized liquid and air are sprayed
by the nozzle through the plasma zone. The arc formed between the electrodes is
pushed down by the biphase flow. Whenever the arc collapses while gliding along
the electrode walls to the end, a new arc will be formed from the initial position
[18].
3.2.2 Materials and Analytical Methods
Triphenylmethane dye Alphazurine A (AA) with the formula of C37H35N2NaO6S2,

azo dye Acid Orange II (AOII) with the formula of C 16H11N2NaO4S, and anthra-
quinone dye Acid Anthraquinone Blue (AAB) with the formula of
C20H13N2NaO5S were prepared. Distilled water was used to make the dye
solutions with desired concentration.
The treated solutions were concentrated to 725 lmol/L for AA, 1429 lmol/L for
AOII, and 1202 lmol/L for AAB (500 mg/L for mass concentration). In the
mixture, the molar concentration is one-third of the molar concentration of the
three kinds of dyes. The mass concentration was still 500 mg/L. The mixture was
treated alone and then added with 5 g zerovalent iron (ZVI). The volume of the
target solution was 500 ml.
The treatments of dye solutions were investigated as functions of the exposure
time t (0, 10, 20, 40 70, and 100 min). The flow rate of feeding gas and feeding
3
solution were 0.8 m /h and 60 ml/min, respectively, and all other working
parameters were kept constant. Discoloration rate was tested by a UV-Vis spec-
trophotometer (Shimadzu UV-2550), while chemical oxygen demand (COD)
measurements were performed by titration according to the Chinese standard
method of COD determination.
COD degradation ratios (D, %) and color removal ratios (R, %) were
calculated as follows:
Þ
D COD0 CODi 100% 3:1
COD ¼ COD0 ð
COD0 and CODi refer to the COD values before and after treatment,
respectively.
Þ
R color ¼ Abs0 Absi 100% 3:2
Abs0 ð
Abs is the absorbance value at the absorbance peak in the visible wavelength
range; Abs0 and Absi are the Abs values before and after treatment, respectively.
3.3.1 Plasma Discoloration and Degradation of Single Dye
The dye solutions for 0, 10, 20, 40, 70, and 100 min of plasma treatment were scanned
by UV-Vis spectrophotometer, and the wavelength of the absorbance peak was
determined in the visible range. The disappearance of the absorbance peaks at 637 nm,
483 nm, and 637 nm in Figs. 3.2, 3.3, and 3.4, respectively, means that the
triphenylmethane groups, azo groups, and anthraquinone groups responsible for
Fig. 3.2 Spectral evolution of plasma-treated AA solution (1, 0 min; 2, 10 min; 3, 20 min; 4, 40
min; 5, 70 min; and 6, 100 min)
Fig. 3.3 Spectral evolution of plasma-treated AOII solution (1, 0 min; 2, 10 min; 3, 20 min; 4, 40
min; 5, 70 min; and 6, 100 min)
Fig. 3.4 Spectral evolution of plasma-treated AAB solution (1, 0 min; 2, 10 min; 3, 20 min; 4, 40
min; 5, 70 min; and 6, 100 min)
the color of AA, AOII, and AAB, respectively, were broken down. Meanwhile, the
absorption band shift from the visible range to the UV or IR region suggested the
formation of new species with simplified structures [19, 20].
In Fig. 3.5, a comparison of the discoloration ratios of AA, AOII, and AAB is
shown, indicating that the discoloration ratios are almost all higher than 90%
(96.55% for AA, 94.66% for AOII, and 89.69% for AAB) after a 100-min
Fig. 3.5 Comparison of the 100

discoloration ratios of three AA
kinds of dyes AOII
Discoloration Ratio (%)

80 AAB
60
40
20
0
0 20 40 60 80 100
Time (min)
treatment. Figure 3.5 also reveals that the discoloration of AAB is faster at first but
then is surpassed by AA and AOII.
COD measurements express the degradation of organic dyes. The abatement of
GAD for AA, AOII, and AAB is shown in Fig. 3.6. The degradation ratios of AOII and
AAB increase when the treatment time increases, while the degradation ratio of
AA decreases at first and increases later. The 100-min abatements by GAD for
AA, AOII, and AAB are 20.4, 35.88, and 41.2%, respectively, which are not as
efficient as discoloration. It should be noted that the AAB degrades faster than
AOII and the AOII degrades faster than AA. They all have potential to be
degraded and can be further decomposed when there is a longer treatment time.
Fig. 3.6 COD abatement

40 AA
evolution of AA, AOII, and AOII
AAB solutions
AAB
30
Degradation Ratio (%)
20
10
-10
-20
0 20 40 60 80 100
Time (min)
Fig. 3.7 The adsorption peaks of mixed dye
3.3.2 Treatment Results of Mixed Dye Wastewater
The mixture of the three kinds of dyes was scanned by the UV-Vis spectropho-
tometer to determine the absorption peaks. The mixture had obvious absorption
peaks at 483 nm and 637 nm, which are the characteristic absorption bands for
AOII and AA and AAB, respectively, as depicted in Fig. 3.7.
When the dye mixture is exposed to the gliding arc plasma, its color started
fading. The discoloration effects can be observed with eyes easily. The color of
the mixed solution changes from the original dark green to light green then to
almost transparent finally, as shown in Fig. 3.8.
The spectra of the treated solutions are recorded (Fig. 3.9) for exposure time t. The
two main peaks decrease with an increase in exposure time and disappear completely
within 70 min, and the absorption value increases largely between 200 and 230 nm,
which were agreed well with the time evolution of pure dye solutions.
Figure 3.10 reveals the color abatement tested at 483 and 637 nm separately.
Discoloration ratios for 483 and 637 nm are 88.26 and 94.94%, respectively,
which are close to the pure dye discoloration ratio (96.55% for AA (absorption
peak: 637 nm), 94.66% for AOII (absorption peak: 483 nm), and 89.69% for AAB
[absorption peak: 637 nm)].
When compared the results of decomposition with bleaching (Fig. 3.11), we can get
the conclusion that the degradation efficiency is inferior to the discoloration efficiency,
which is only 17.96% after a 100-min treatment. However, we can also find that the
curve for discoloration rate closes horizontally after being treated with a 70-min
treatment, while the curve for degradation ratio still has a trend to grow, as shown in
Fig. 3.11. It can be degraded further hopefully.
Fig. 3.8 Color change of treated solution with an increase in treatment time (solutions were
diluted for five times)
Fig. 3.9 Spectral evolution of plasma-treated mixed dye solution
3.3.3 Discoloration and Degradation in the Presence

of Zerovalent Iron (ZVI)
The plasma discharge allows an accumulation of H 2O2 in the solution. The treated
dye solution has an acidic property. Hence, these two features correspond with the
requirements of Fenton reaction. The Fenton reaction can be realized by
introducing ferrous ions into the device. Zerovalent iron (ZVI) was used to
produce efficient amount of ferrous ions through the following reactions [18]:
Fig. 3.10 Discoloration 100 483nm

ratios at the wavelength of 637nm
483 nm and 637 nm
Ratio(%)
80
Discoloration
60
40
20
0 20 40 60 80 100
Time (min)
20
Fig. 3.11 Comparison of

discoloration ratios and 100
degradation ratios
Ratio(%)
Ratio (%)
80 16
60 12
Discoloraion
40 8
Degradation
20 483nm 4
637nm
Degr. Ratio 0
0
0 20 40 60 80 100
Time (min)
0 þ 2þ ð3:3Þ
Fe þ 2H ! Fe + H2
0 3þ 2þ ð3:4Þ
Fe þ 2Fe ! 3Fe
Then, the Fenton oxidation process utilizes the ferrous ion produced by ZVI and
H2O2 emitted by GAD:
2þ 3þ
Fe þ H2O2 ! Fe þ OH þ OH ð3:5Þ
Therefore, the catalysis process that combines Fenton reaction with gliding arc
plasma treatment can improve the efficiencies of GAD treatment.
Zerovalent iron was added to absorb the dye mixture 24 h before the treatment.
ZVI came from the industrial waste that will be discarded if not be reused. The
Fig. 3.12 Absorption of the mixed dye before and after (24 h) adding ZVI
solution concentration was effected slightly by the addition of ZVI, as illustrated

in Fig. 3.12. This change is caused by the absorption characteristic of ZVI that has
a limited absorption capacity.
After a 100-min treatment, when compared the discoloration ratios with the
results of the mixed dyes without ZVI (Fig. 3.13), the final degradation ratio of the
solution with ZVI is just a little higher than the solution without ZVI. The dashed
lines grow not as fast as the solid lines in the first 10 min, but later, they start to
speed up. The result is that the degradation ratios are almost the same for 483 and
637 nm at 40 min. After some time, the growth of both ratios gets to slow down
closing to a limited value. In the initial phase of treatment, the ZVI shows little

discoloration ratio between
mixed dyes with and without
ZVI 80
Discoloration Ratio (%)
60
40
483nm without ZVI
20 637nm without ZVI

483nm with ZVI
637nm with ZVI
0
0 20 40 60 80 100
Time (min)
effect that can be observed by the catalytic reaction trend. It is probably due to the
acidity in the solution that is not low enough to oxidize ZVI to ferrous. The
original pH of the mixed solution was 7.65, and it dropped up to 3.20 with only
10-min treatment. The acidity environment met the optimal requirements (pH =
2–3 and ferrous ions) of Fenton reaction through the 20-min treatment. Therefore,
the promoting effect of ZVI becomes significant in the intermediate phase. Finally,
the effect declines during the last phase, in which the mixed dye was about to be
discolored completely.
The kinetics of discoloration by GAD treatment of mixed dyes by adding ZVI is
shown in Fig. 3.14. The bleaching kinetics follows a pseudo-first-order kinetics and
Abs 0
can be verified by the linear fitting of ln Abst ¼ kt with the correlation coefficient
2
(R ) values of 0.9823 and 0.9858. The kinetic constants of discoloration are 0.0301
−1
and 0.0385 min for 483 and 637 nm, respectively, as represented by the slopes
in Fig. 3.14.
Being different from the discoloration ratios, the values of the degradation ratios
for dye mixture with and without ZVI are not quite alike. As given in Fig. 3.15, the
dye mixture with ZVI was degraded much faster than the mixture without ZVI and the
100-min degradation value of red line can be 44.18% higher than the black lines even
though they are quite close at the initial 10 min, which can also be explained with the
acidity situation in the solution. On the other hand, it is also obvious that there is a
potential growth for both kinds of dye mixtures. Degradation consumes more time
than discoloration, since the discoloration happens before degradation. The complex
organic chemical was decomposed into small organic chemical by treatment first and
then degraded into inorganic compounds [21].
The graph of ln(COD0/CODt) versus treatment time (Fig. 3.16) of mixed dyes
with and without ZVI shows two fitting straight lines, whose slopes represent the
Fig. 3.14 The discoloration 4.0 y=0.0385x-0.0442

kinetics of mixed dyes with 3.5 483nm
ZVI 637nm 2
R =0.9858
3.0
2.5
Ln( A /A)
2.0
1.5
y=0.0301x-0.0787
1.0 2
R =0.9823
0.5
0.0
0 20 40 60 80 100
Time (min)

dye mixture COD abatement Dye Mixture
with and without ZVI 60 0
Dye Mixture with Fe
Degradation Ratio (%)

50
40
30
20
10
0
0 20 40 60 80 100
Time (min)
Fig. 3.16 Comparison of the 1.2 mixed dyes

degradation kinetics of dye
mixed dyes with ZVI
mixture with and without ZVI
1.0 y=0.0101x-0.0839
)/COD
0.8 2
R =0.9713
0.6
(LnCOD 0
0.4
y=0.0019x+0.0003
0.2 2
R =0.97128
0.0
0 20 40 60 80 100
Time (min)
−1
kinetic constants of degradation. The constant is 0.0101 min for the solution
with ZVI, which is more than five times than the constant for the solution without
−1
ZVI (0.0019 min ). This implies a strong potential for the combination of GAD
treatment and Fenton reaction.
From the graphs and descriptions above, we can conclude that ZVI played a vital
role in increasing the discoloration and degradation ratios. We set two groups of ZVI,
namely ZVI X and ZVI Y. They were cleaned and dried. The original weight of both
ZVI X and ZVI Y were 5 g. After immersing ZVI X and ZVI Y in mixed dye for 24 h,
treat ZVI X with GAD plasma for 100 min (ZVI Y was immersed in mixed dye all the
time until the end of GAD plasma treatment of ZVI X) and
Table 3.1 Comparison of different research studies and their major results

Plasma Materials Method of treatment Type of dyes Major results Highlight References
type used Discoloration k (min
−1 )
Degradation k
ratio (%) ratio (%) −1
(min )
Pulsed None Streamer Rhodamine B 40 (120 min) – – – The spark-streamer [22]
discharge Spark 73 (120 min) mixed discharge
plasma Spark with streamer 97 (120 min) mode was most
effective. The other
physical effects, such
as shock waves and
ultraviolet radiation,
play an important
role in the
decoloration process
Pulsed None Threat with Amaranth 81.24 0.0269 15 (120 min) – Decolorization is a [23]
discharge non-thermal plasma (30 min) (pH > 10) TOC fast process, whereas
plasma supplied with bipolar mineralization is
pulse power attained after a long
period of time. It
requires considerable
amount of energy to
attain the complete
mineralization
Pulsed None Multi-needle-to-plate Acid orange 7 8.8 (24 kV, – – – The decoloration [24]
corona high-voltage 50 Hz) rate increases with
discharge discharge for 60 min 56.1 (30 kV, increasing peak
plasma 50 Hz) pulse voltage and
61.7 (30 kV, pulse frequency,
25 Hz) presumably due to
94.8 (30 kV, the increased electric
75 Hz) field energy
(continued)
33
34
Table 3.1 (continued)
type used Discoloration k (min −1 )
Degradation k
(min )
GAD None Treated by Orange I Crystal 95 (30 min) 0.886 92%, 75%, 83% 0.0173 It is proved that the [25]
atmospheric pressure Violet 89 (30 min) 0.042 (120 min) 0.024 plasma treatment is
plasma Eriochrome 88.4 (60 min) 0.083 COD 0.0296 efficient and induces
…
3 Degradation and Discoloration of Textile Dyes Using Gliding Arc
Black T the bleaching of the
target solution first
and then the
degradation of the
organic solute
GAD Sodium Gliding electric Bromothymol 60.6 (5 min) – – – Adding sodium [15]
azide, discharge at Blue 94 (with azide to the dye
hydrogen atmospheric pressure added H2O2, solution limits the
peroxide 5 min) discoloration
99.1 (10 min) process. The
68.2 (with presence of added
NaN3 added, hydrogen peroxide
10 min) markedly increases
discoloration rate
GAD Inorganic Plasma treated for Alizarin red S All above 80 0.014 All above 61% 0.008 The addition of [5]
salts 120 min Orange G 0.013 COD 0.010 sulfate ions slightly
Mixture I, II, enhanced the
III, IV discoloration rate of
Mixture with dye mixture,
inorganic salts compared to chloride
ions. COD
measurements are
particularly affected
when the salts are
proportionally mixed
(continued)

Degradation k
(min )
+ 0
GAD Fe2 , Fe Plasma treated for Acid Orange 7 80 (38 min) 0.043 35.4% – ZVI exhibited a [18]
2+
40 min AC7 with Fe 80 (34 min) 0.047 (40 min)— better catalytic effect
0
AC7 with Fe 80 (25 min) 0.056 41.6% (40 min) in GAD plasma than
COD ferrous ions. The
decolorization
reactions of AO7
followed
pseudo-first-order
kinetic model
GAD TiO2 Non-thermal gliding Textile 88.2 – 100.0% 0.013 The TiO2-mediated [21]
catalyst arc technique coupled wastewater: (TiO2 dose: (TiO2: 3 g/L) 0.033 gliding arc discharge
with photo catalyst Before 3 g/L) 100.0% (TiO2) (GADTiO2) showed
purification 95.9 (TiO2: 3 g/L) 0.012 potential application
treatment (TiO2 dose: COD 0.052 for the treatment of
After local 3 g/L) (TiO2) liquid wastes,
treatment resulting in the
mineralization of the
wastewater samples
confirmed by
chloride, sulfate, and
phosphate ion
formation
(continued)
35
36
Degradation k
(min )
GAD TiO2 Non-thermal GAD at Anthraquinonic 46% (15 min) 0.045 84% (180 min) 0.0103 The use of the [26]
atmospheric pressure acid green 25 totally 0.455 93% 0.043 catalyst TiO2
(15 min, (2 g/L (180 min,2 g/L (2 g/L improved
…
3 Degradation and Discoloration of Textile Dyes Using Gliding Arc
2 g/L TiO2) TiO2) TiO2) TiO2) decolorization, just
as degradation,
occurring at a faster
rate than in the TiO2-
free case
GAD ZVI Humid air discharge Alphazurine A 96.55 – 20.40 – Gliding arc plasma This paper
for 100 min Acid Orange II 94.66 35.88 treatment is effective
Acid 89.69 41.20 to triphenylmethane
Anthraquinone 484/637 nm 17.96 dye, azo dye, and
Blue 88.26/94.97 62.14 anthraquinone dye.
Mixture 93.87/97.35. COD With the addition of
Mixture(with ZVI, both the
ZVI) discoloration and
degradation ratios
grow
expose ZVI X and ZVI Y for 1 h in the air. In The treated ZVI was slightly rusty
and the untreated seemed to be the same, as was before the treatment. ZVI X was
obviously rusty, while ZVI Y was only slightly rusty 24 h after the treatment. The
treated ZVI X was corroded heavily by GAD plasma treatment, thus reacting
easily with the oxygen in the air.
Adding iron would increase the discoloration and decomposition rates, espe-
cially the degradation rate that can be raised up to five times of that without ZVI
before. Added ZVI can make use of H 2O2 and the acid environment created by
GAD to produce more OH, which improves the oxidation efficiency. The GAD
treatment and Fenton reaction work together: GAD treatment is strengthened by
the ZVI catalyst and the requirements for Fenton reaction are met because of
GAD plasma.
3.3.4 Comparison of Different Research Studies and Their

Major Results
See Table 3.1.
3.4 Conclusions
Exposure of triphenylmethane dye (Alphazurine A), an azo dye (Orange G), an

anthraquinone dye (Acid Anthraquinone Blue), and their mixture to gliding arc
plasma has shown efficiency in the GAD treatment for the discoloration and
degradation of the dyes. The catalysis characteristics of ZVI were also studied.
Based on the present experimental results, the conclusions can be summarized
as follows. Gliding arc plasma treatment is effective in triphenylmethane dye, azo
dye, and anthraquinone dye, which are often used in the textile industry. The
discol-oration ratios are quite high, with around 90%. The degradation rates are
not as high as the former and are lower than 40% at most times. The condition of
both the rates is also same with the mixture of the three dyes.
While adding ZVI, the plasma-induced condition enables the Fenton reactions
to take place and both the discoloration and degradation ratios grow, especially the
2+
degradation ratio by 42%. The continuous production of Fe from ZVI can
sustain the Fenton reactions, thus obviously increasing the treatment efficiency.
ZVI works as a catalyst in the process. Additionally, the gliding arc discharge
plasma with the addition of ZVI causes no harm to either environment or human
health, and ZVI can be collected from the industrial wastes. Thus, the GAD
treatment combined with Fenton reaction by the catalysis process can be used for
dye treatment on a large scale in the future.
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21. Ghezzar MR, Abdelmalek F, Belhadj M, Benderdouche N, Addou A. Enhancement of the
bleaching and degradation of textile wastewaters by gliding arc discharge plasma in the
presence of TiO2 catalyst. J Hazard Mater. 2009;164(2–3):1266–74.
References 39
22. Sugiarto AT, Ito S, Ohshima T, Sato M, Skalny JD. Oxidative decoloration of dyes by pulsed
discharge plasma in water. J Electrostat. 2003;58(1–2):135–145.
23. Zhang RB, Zhang C, Cheng XX, Wang LM, Wu Y, Guan ZC. Kinetics of decolorization of
azo dye by bipolar pulsed barrier discharge in a three-phase discharge plasma reactor.
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24. Wang H, Li J, Quan X. Decoloration of azo dye by a multi-needle-to-plate high-voltage
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25. Abdelmalek F, Ghezzar M. Bleaching and degradation of textile dyes by nonthermal plasma
process at atmospheric pressure. Ind Eng Res. 2006;45(1):23–9.
26. Ghezzar MR, Abdelmalek F, Belhadj M, Benderdouche N, Addou A. Gliding arc plasma
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Appl Catal B-Environ. 2007;72(3–4):304–13.
Chapter 4
Reduction and Removal of Cr(VI) from
Aqueous Solution by Microplasma
Abstract In this chapter, the reduction and removal of Cr(VI) from aqueous solution by
microplasma are explained, which represents a new and fascinating realm of plasma
science for the first time. The effect of various process parameters on the Cr(VI)
reduction efficiency and the effect of initial pH and ethanol on the removal of Cr(VI)
are systematically examined. The optimum condition for Cr(VI) reduction was initial
pH at 2 with stir where the microdischarge gas was argon with the flow rate of 60
mL/min. The reduction efficiency of Cr(VI) increased with an increase in input power
but decreased with an increasing initial concentration of Cr (VI). In particular, additive
hydroxyl radical scavenger (ethanol) greatly improved the reduction efficiency and
facilitated the removal of chromium dissolved in the solution. The best removal
efficiency was obtained when the pH was 6. In addition, the energy efficiency of
−4
microplasma to reduce Cr(VI) is 2.0 10 mg/J and is comparable to that in
electrolysis and other forms of glow discharge. The advan-tages, such as low cost,
scalability, and easy operating techniques, of this approach have broad prospects in
water treatment (Xiao in Removal of hexavalent chromium in water and preparation of
cuprous oxide nanoparticles by microplasma. Yat–sen University, 2012, [1]; Du in
Non-Thermal arc plasma technology and application. BeiJing: Chemical Industry
Press, 2015, [2].
Keywords Microplasma Chromium(VI) Reduction Removal Mechanism
4.1 Introduction
Chromium exists in large amounts in the wastewaters of leather tanning, pigment and
fertilizer productions, electroplating, metallurgy, and other industries. Although Cr can
exist in oxidation states ranging from Cr(II) to Cr(VI), trivalent chromium
3656-9_4
42 4 Reduction and Removal of Cr(VI) from Aqueous Solution …
(Cr(III)) and hexavalent chromium (Cr(VI)) are the most dominant oxidation
states in the natural environment [1]. Cr(III) is an essential nutrient at trace level
and has lower solubility in water. In contrast, Cr(VI) is highly toxic, mutagenic,
and potentially carcinogenic to living organisms [3]. Therefore, it is necessary to
reduce Cr(VI) to Cr(III) with subsequent immobilization as hydroxide when
disposing Cr (VI)-contaminated wastewater [4].
Current technologies for treatment of Cr(VI)-containing wastewaters include ion
exchange, reduction, adsorption, membrane separation, solvent extraction, and
electrodialysis [5–12]. Among them, the conventional method of reduction using
chemicals, such as sulfur dioxide or sodium metabisulfite, is easy to implement but
produces additional pollution due to the ultra use of reducing chemicals and the
production of poisonous by-products [13]. Adsorption is another widely used method.
The adsorbent of this method needs to be regenerated, which is sometimes a very
inconvenient procedure [14]. Ion exchange and electrodialysis are efficient for Cr(VI)
reduction, but the expense is comparatively high. Furthermore, mem-brane techniques
and solvent extraction meet the challenge about the removal of lower concentrations of
metals from the solution [15]. These methods have led to the development of
alternative technologies for treating chromium species in wastewaters. In the recent
years, some researchers have investigated discharge plasma in contact with liquids for
removal of Cr(VI)-containing solutions [13, 16– 18]. However, all of them have used
stainless steel electrode, which contains iron, and the iron can dissolve in wastewater
and cause Fenton reaction, thus disturbing the reduction effect of plasma itself. In
addition, their consumption of argon gas is very high and being wasted. Based on these
considerations, it is of great practical and research interest to use miniaturization of
plasma, i.e., microplasma, which is the newest discharge form for removing Cr(VI) in
wastewater treatment.
Microplasma is a special subdivision of electrical discharges formed in
electrode geometries, where at least one dimension is less than 1 mm [19].
Microscale plasmas have attracted enormous interest from the plasma organization
due to their characteristics of small physical size, excimer generation, atmospheric
pressure stability, and non-equilibrium thermodynamics [20–25]. These properties
make microplasmas suitable for a wide range of applications, including medicine,
gas treatment, textiles, surface modification, and nanofabrication [26]. To the best
of our knowledge, this is the first study that utilizes microplasma to treat
wastewater, particularly in removal of Cr(VI)-containing solutions.
In this chapter, a DC microplasma that takes place at the gas–solution interface
is utilized to reduce and remove aqueous Cr(VI). This study mainly investigates
the Cr(VI) reduction efficiency under various process parameters, such as initial
pH with or without stir, gas flow, initial concentration of Cr(VI), input power, type
of discharge gas and an addition of ethanol that is severed as hydroxyl radical
scav-enger, and the effect of Cr(VI) removal in the presence of ethanol. The
sediment was characterized by FTIR and XRD, and the possible reaction
mechanisms are discussed.
4.2 Experimental Details 43
4.2 Experimental Details
4.2.1 Discharge Apparatus and Materials
The experimental setup for microplasma reduction and removal of Cr(VI)-con-

taining solutions is shown in Fig. 4.1. A stainless steel tube (0.7 mm inside
diameter and 8 cm length) was positioned 3 cm away from the tungsten bar elec-
trode (2 mm diameter and 15 cm length) with a gap of 2 mm between the tube end
and the liquid surface. Argon gas flow was coupled with the tube and controlled by
a glass rotameter. The stainless steel tube acted as anode, and the tungsten bar as
cathode. The reactor was made of common glass, with an inner diameter of 5.5 cm
and a length of 8.5 cm. Potassium dichromate (K 2Cr2O7) dried at 110 °C for 2 h
was used to prepare the desired concentration of simulant wastewater. The initial
pH value was adjusted by using 20% (V:V) H 2SO4 and 1 M NaOH. All chemicals
were commercially available in the analytical and guaranteed grade. When a high
voltage (*2500 V) was applied, the microplasma was formed at the gas–solution
interface and then kept stable by a ballast resistor (R = 10 kX) and, finally, the
current was kept at about 40 mA and the voltage was lowered to approximately
1000 V (10%). During the treatment, the solution was gently stirred with a mag-
netic stirrer for acquiring the best reduction efficiency. For the experiments with
additives, certain percentage of ethanol was added to the solutions initially.
Fig. 4.1 The schematic diagram of a minimized non-thermal arc plasma reactor
4.2.2 Analyses
The diphenylcarbazide (DPC) was used as the color reagent to colorimetrically

determine the concentration of Cr(VI) remaining in the solution [27]. The absor-
bance at wavelength of 540 nm was monitored by an ultraviolet–visible spec-
trometer (T6 New Century, Persee). The total Cr was examined by flame atomic
absorption spectroscopy (FAAS, Z-2000, Hitachi) with a minimum detection limit
of 0.03 mg/L. The content of H 2O2 produced from the discharge-treated solution
was determined spectrophotometrically at 385 nm, after mixing with titanium
potassium oxalate in acidic condition [28]. The production of nitrate was
measured by ion chromatography (882, Metrohm). After treating in the presence
of ethanol, the sediment was extracted by centrifuge (HC-3018, Zonkia) and
heated at 55 °C and 400 °C for 1 h. Prepared samples were finally characterized by
an FTIR spectrometer (EQUINOX 55, Bruker) and an X-ray diffractometer
(D/Max-IIIA, Ragiku). In addition, an elementar analyzer (Vario EL, Elementar)
was used to analyze the sediment element. Waveforms of the voltage and current
were mea-sured by a digital oscilloscope (TDS2024B, Tektronix).
4.3 Results
4.3.1 Effect of Gas Flow Rate on Cr(VI) Reduction
In this section, the discharge gas flow rate on the reduction of Cr(VI) in aqueous
solutions was investigated. It is hard to generate the microplasma if the velocity is
too little. Because of the small gap between gas outlet and liquid surface, gas with
the larger flow rate will make the solution splash onto the wall of container, which
makes the discharge instability. Therefore, the reported range of gas flow rate from
40 to 200 mL/min was chosen. As shown in Fig. 4.2, the reduction efficiency
Fig. 4.2 Effect of gas flow 1.2

Relative concentration of Cr(VI)
rate on Cr(VI) reduction by 1.0 40 ml/min

argon microplasma discharge 60 ml/min
0.8
([Cr(VI)] = 40 mg/L, volume 80 ml/min
= 25 mL, discharge time = 5 0.6 100 ml/min
min, and pH = 2, with 150 ml/min
stirring) 0.4 200 ml/min
0.2
0.0
0 1 2 3 4 5
Time (min)
4.3 Results 45
increased with the increasing flow rate from 40 to 60 mL/min and from 80 to
200 mL/min, and the best efficiency was obtained at 60 mL/min, indicating the
fact that the larger gas flow rate does not cause the better treatment efficiency.
4.3.2 Effect of Initial pH on Cr(VI) Reduction
In the present study, 25 mL of the K2Cr2O7 simulant wastewater at concentration of

40 mg/L Cr(VI) with varying initial pH values from 2.0 to 11.0 was poured into the
reaction vessel for microplasma treatment without stirring. The sample of 1 mL from
the solution was regularly drawn to determine the residual Cr(VI). Figure 4.3 shows
the effects of initial pH on Cr(VI) reduction by microplasma. The reduction
effectiveness was enhanced with increasing initial pH value from 5 to 11, as shown in
Fig. 4.2, while the best effectiveness was obtained under the condition of strong acid.
Only 90% of Cr(VI) can be reduced with a 4-min microplasma treatment when the
initial pH is 9.0, while nearly all of Cr(VI) can be reduced when the initial pH is 2.0
within the same treatment time. Surprisingly, at the end of discharge treatment for 10
min, almost 100% Cr(VI) were reduced in alkaline solution, which was different from
most of the previously reported cases [16, 29, 30]. Unexpectedly, already reduced
Cr(VI) was partially oxidized back to Cr(VI) at the last several minutes of
microplasma treatment at the initial pH values of 5 and 7. However, the degree of the
oxidation was higher in mild acid conditions than that in neutral conditions. The
control experiments with different initial pH values from 2 to 11 in the absence of
microplasma discharge were also conducted.
Relative concentration of
ofCr(VI)
1.2 1.2
Cr(VI) 1.0 1.0
concentration
0.8
0.8 0.6
0.6 0.4
0.2
Relative
0.4 pH=2 0.0 pH

0 2 4 6 8 10 12
0.2 pH=5
pH=7
0.0 pH=9
pH=11
0 2 4 6 8 10
Time (min)
Fig. 4.3 Effect of initial pH on Cr(VI) reduction by argon microplasma discharge ([Cr (VI)] = 40
mg/L, volume = 25 mL, discharge time = 10 min, and argon flow rate = 60 mL/min; inset is the
effect of pH on Cr(VI) reduction without discharge: [Cr(VI)] = 40 mg/L, volume = 25 mL, and
reaction time = 20 min, without stirring)
4.3.3 Effect of Stirring on Cr(VI) Reduction
It can be found that using stirrer will not lead to the instability of microplasma
discharge. The results of stirring effect on Cr(VI) reduction are shown in Fig. 4.4.
It is indicated that the reduction rate with stirring was faster than that without
stirring. Almost 100% Cr(VI) in solution with stirring was reduced within 2 min
of dis-charge treatment, but it was only 92% for no stirring conditions.
4.3.4 Effect of Initial Cr(VI) Concentration on Cr(VI)

Reduction
Different initial Cr(VI) concentrations ranging from 20 to 100 mg/L by 20 mg/L steps
are prepared and treated by the microplasma. The effect of initial Cr(VI) concentration
on its reduction at initial pH value of 2.5 is shown in Fig. 4.5. Higher initial
concentration resulted in relatively lower Cr(VI) reduction efficiency.
4.3.5 Effect of Various Discharge Gas on Cr(VI) Reduction
In this section, the role of discharge gas on the reduction of Cr(VI) in aqueous
solutions was investigated. Three gases (argon, air, and nitrogen) were tested at the
flow rate of 60 mL/min. As the feeding gas, the reduction rate during the micro-plasma
treatment was higher for argon, which was in turn followed by air and then nitrogen,
though there was only a little difference between them [31] (Fig. 4.6).
Fig. 4.4 Effect of stirring on

1.2
Cr(VI) reduction by argon
microplasma discharge ([Cr 0.9
(VI)] = 40 mg/L, without stirring
volume = 25 mL, discharge with stirring

time = 5 min, pH = 2, and 0.6
argon flow rate = 60 mL/min)
0.3
0.0
0 1 2 3 4 5
Time (min)
4.3 Results 47
Fig. 4.5 Effect of initial Cr
Cr(VI)
1.2 20 mg/L
(VI) concentration on Cr(VI)
of
1.0 40 mg/L
reduction by argon micro
60 mg/L
plasma discharge
nconcentratio
0.8 80 mg/L
(volume = 25 mL, discharge 0.6 100 mg/L
time = 5 min, pH = 2.5, and
argon flow rate = 60 mL/min, 0.4
with stirring)
Relative
0.2
0.0
0 1 2 3 4 5
Time (min)
Fig. 4.6 Effect of various Cr(VI) 1.2

discharge gas on Cr(VI)
of
1.0 Ar
reduction by microplasma
discharge ([Cr (VI)] = 60
concentration
0.8 Air
mg/L, N
0.6
volume = 25 mL, discharge 2
time = 5 min, pH = 2.5, and 0.4

gas flow rate = 60 mL/min,
Relative
with stirring) 0.2
0.0
0 1 2 3 4 5
Time (min)
4.3.6 Effect of Input Power on Cr(VI) Reduction
Input power is a key parameter for the reduction of hexavalent chromium. This
experiment investigated the Cr(VI) reduction under different input powers. As shown
in Fig. 4.7, 57, 69, and 78% of aqueous Cr(VI) were reduced after the 2-min
Fig. 4.7 Effect of input power

1.2
on Cr(VI) reduction by argon 1.0 34.8W
microplasma discharge
([Cr(VI)] = 60 mg/L, volume 0.8
40.4W
= 25 mL, discharge time = 5 0.6 50.0W
min, pH = 2.5, and argon
flow rate = 60 mL/min, with 0.4
stirring)
0.2
0.0
0 1 2 3 4 5
Time (min)
microplasma treatment for the input powers 34.8, 40.4, and 50 W, respectively.
The Cr(VI) reduction rate increased with the increasing input power. However, if
the input power is over 50 W, the tip of stainless steel tube will melt and will be
out of shape. Therefore, 40.4 W is chosen as the optimum input power in the
present study.
4.3.7 Effect of Ethanol on Cr(VI) Reduction and Removal
Adding the hydroxyl radical scavenger to the solution at the beginning of micro-
plasma treatment was used to investigate the mechanism of Cr(VI) reduction. In
this study, the additive ethanol was used as OH scavenger. As illustrated in Fig.
4.8, ethanol showed a positive effect on Cr(VI) reduction. The reoxidation
phenomenon no longer appeared when 1% (V:V) ethanol was added to the
solution, and higher percentage (>99%) of Cr(VI) reduction was obtained after
discharge reduction for 10 min.
Surprisingly, the solution became turbid during the discharge treatment when
ethanol was added. After treatment, the sediment was deposited in the remaining
solution slowly. With the help of centrifuge, the obtained supernatant was used to
determinate the total Cr by AAS and the sediment was used to characterize by an FTIR
spectrometer and an X-ray diffractometer. It was identified that the total Cr content in
the supernatant decreased observably. This manifests that the existence of ethanol
facilitated not only the Cr(VI) reduction but also the removal of total Cr from the
solution. In addition, we also studied the effect of ethanol concentration varying from
0.5 to 10% (V:V) on Cr removal through batch experiments with fixed volume (25
mL) and initial pH (5) of K2Cr2O7 solution at the concentration of
Relative concentration of 1.2

Cr(VI)
1.2
Cr(VI)
of
1.0
0.9 0.8
concentration
0.6 0.2
0.6
Relative
0.4
0.3 0.0 Ethanol percentage (%,V:V)
0 2 4 6 8 10
0.0 without ethanol

with ethanol
0 2 4 6 8 10
Time (min)
Fig. 4.8 Effect of ethanol on Cr(VI) reduction by argon microplasma discharge ([Cr
(VI)] = 40 mg/L, volume = 25 mL, discharge time = 10 min, pH = 5, and argon flow rate = 60
mL/min, without stirring; the inset is the effect of ethanol on Cr(VI) reduction without
microplasma discharge: [Cr(VI)] = 40 mg/L, total volume = 25 mL, and reaction time = 20 min)
4.3 Results 49
Fig. 4.9 Effect of ethanol
of total Cr
0.8
percentage on Cr(VI) removal
by argon microplasma 0.6
discharge ([Cr
efficiency
(VI)] = 100 mg/L, 0.4
volume = 25 mL, discharge
time = 10 min, pH = 5, and
Removal
0.2
argon flow rate = 60 mL/min,
with stirring) 0.0
0 2 4 6 8 10
Ethanol percentage (%,V:V)
100 mg/L Cr(VI), as depicted in Fig. 4.9. The quantity of Cr(VI) removed from
the solution increased with the increasing ethanol concentration, and the
maximum removal efficiency (77.4%) was acquired when the ethanol percentage
achieved 2% (V:V). Furthermore, it can be seen that the removal efficiency was
almost the same when the concentration of ethanol was larger than 2%.
4.3.8 Effect of Initial PH on the Removal of Cr(VI)

in the Presence of Ethanol
The pH also plays a significant role in the removal of Cr(VI) [32, 33]. In the present
study, 25-mL Cr(VI)-containing solutions at the concentration of 100 mg/L with
different initial pH values from 2 to 11 were disposed by microplasma for inves-
tigating the pH effect on Cr(VI) removal. By using the reported method in Sect. 4.3.5,
the results are presented in Fig. 4.10. The best Cr(VI) removal effi-ciency was
obtained when the initial pH was 6, as shown in Fig. 4.10. Before this pH value, the
removal efficiency increased with an increase in pH value. At the pH value of 7, the
efficiency was also in high level. However, once the solution was
Fig. 4.10 Effect of initial pH

Removal efficiency of total Cr
0.8
on the removal of Cr(VI) in
the presence of 2% ethanol
([Cr(VI)] = 100 mg/L, 0.6
volume = 25 mL, discharge
time = 10 min, and argon 0.4
flow rate = 60 mL/min, with
stirring) 0.2
0.0
1 2 3 4 5 6 7 8 9 10 11 12
pH
changed to alkaline, i.e., pH ranged from 8 to 11, the effect of ethanol on the removal
of Cr(VI) appeared very weak. This can also be observed visually that no sediment
was generated during the treatment in that situation. It is noteworthy that the optimal
pH value for Cr removal was quite different from the optimal initial pH value for
Cr(VI) reduction. The former was around 6, and the latter was between
2 and 9.
4.3.9 Characterization of the Sediment
An FTIR analysis (Fig. 4.11) and a powder XRD analysis (Fig. 4.12) on the sedi-
ment that was dried at different temperatures (at 55 °C and/or 400 °C for 1 h)
−1
were also performed. As shown in Fig. 4.11a, the strong peak near 520 cm was
−1
due to the Cr–O lattice vibration. A broad peak at about 850 cm was due to the
out-of-plane bending vibrations of carbonate. In addition, the spectra contained
Fig. 4.11 FTIR spectra of the (a) 120

sediment after heating at 55
°C (a) and 400 °C (b) for 1 h
(%)
90
Transmittance
30
60
0
0 1000 2000 3000 4000

Wavenumber (cm-1)
120
(b)
90
Transmittance (%)
60
30
0
0 1000 2000 3000 4000
Wavenumber (cm-1)
4.3 Results 51
−1
prominent peaks corresponding to coordinated or adsorbed H 2O (near 1630 cm ) and
−1
carbonate (near 1498 cm ). The stretching of surface hydroxyls originated from
dissociative chemisorptions of water to the OH stretching of the non-dissociated water
molecules [34]. The H2O and carbonate bands appearing in this spectrum are due to
−1
the strong affinity of Cr(OH)3 for both substances [34]. The bond at 3400 cm is due
to the stretching of surface hydroxyls originated by dissociative water chemisorption
and the OH stretching of non-dissociated water molecules [35, 36]. According to the
main features of these spectra and the X-ray diffraction pattern, as shown in Fig. 4.12a,
we inferred that the main component of the sediment is Cr(OH) 3. Figure 6(b) shows
that the spectrum of the sediment dried at 400 °C for 1 h. The sample did not have any
−1
significant absorption band in the region 1300–4000 cm . The strong peaks at 557
−1
and 620 cm were known as the main characteristic peaks of chromic oxide (Cr 2O3)
[36]. Figure 4.12 presents the diffractograms of the sediment dried at different
temperatures [55 °C (a) and 400 °C (b)]. The diffractograms were retrieved using the
JADE 5.0 software. The searching
Fig. 4.12 XRD pattern of the (a) 3000

sediment after heating at 55
°C (a) and 400 °C (b) for 1 h
2500
Intensity (a.u.)
2000
1500
1000
500
20 40 60 80
2theta (deg)
(b) 3000
Intensity (a.u.) 2000
1000
0
20 40 60 80
2theta (deg)
results indicated that the main constituent was Cr2O3 in the sediment after heating at
400 °C for 1 h. This further demonstrates that the main component of the sediment is
Cr(OH)3 that can be decomposed into Cr2O3 when heating at high temperature [36].
4.4 Discussion
When the microplasma is generated at the solution surface, energetic ions,

radicals, and electrons are formed to reduce Cr(VI) in the solution [37]. The
reaction path for the formation of these reactive species in the solution is
explained as follows [13, 16]:
þ þ
H2O þ nH2O ! H3O þ nOH þ ð n 1ÞH ð4:1Þ
+
where n represents the non-Faraday value [38] and H2O is produced by high-
energy electron bombardment with H2O molecules. Then, these radicals combine
with each other:
OH þ H ! H2O ð4:2Þ
OH þ OH ! H2O2 ð4:3Þ
H þ H ! H2 " ð4:4Þ
Among the produced reactive species, hydrated electron, hydrogen radical, and
hydrogen peroxide can reduce the existing Cr(VI) in the solution in appropriate
conditions [39, 40]:
2 þ 3þ ð4:5Þ
Cr2O7 þ 14H þ 6e ! 3Cr þ 7H2O
2 þ 3þ ð4:6Þ
Cr2O7 þ 8H þ 6H ! 2Cr þ 7H2O
þ 3þ ð4:7Þ
2HCrO4 þ 3H2O2 þ 8H 2Cr þ 3O2 þ 8H2O
The reduction of Cr(VI) by H2O2 is thermodynamically beneficial due to the

standard electrode potentials: +0.56 V versus standard hydrogen electrode (SHE)
for H2O2 oxidation and +1.08 V vs. SHE for the Cr(VI) reduction at the pH value
of 2.0.
Cr(VI) is mainly represented in various forms, such as H 2CrO4, HCrO4−, CrO42−, and
Cr2O72−, in the solution as a function of pH. The equilibrium of Cr(VI) speciation
affected by solution pH is explained with the following formulas [41]:
4.4 Discussion 53
2 þ ð4:8Þ
HCrO4 $ CrO4 þ H ; pKa ¼ 5:9
þ ð4:9Þ
H2CrO4 $ HCrO4 þ H ; pKa ¼ 4:1
H O $ 2HCrO ; pK a ¼ 2:2
Þ
CrO2 ð 4:10
2 þ 2 4
7
− 2−
In acidic solution (2 < pH < 6), HCrO4 and Cr2O7 are in equilibrium. In
neutral or basic solution (above pH = 6), the predominant species is the yellow
2−
chromate anion (CrO4 ) [42].
The Cr(VI) reduction rate increases as the solution pH decreases, since the rate
2− 2 −
constant of the reaction Cr2O7 and H is higher than that of CrO 4 and H. In
addition, oxidation potential of Cr(VI) increases with the decrease in pH value in
the solution. Therefore, an acidic condition is more suitable for reducing Cr(VI)
than the neutral or basic conditions [43].
As shown in Fig. 4.2, the effect of pH on Cr(VI) reduction displayed in our study is
different. The reduction efficiency increases with decreasing pH from 5 to 2 and with
increasing pH from 7 to 11. Specifically, the reoxidation occurred at the last few
minutes, where the initial pH was 5 and 7, which was not reported in Ke’s work [18].
For further investigation, 1 mL of the treated solution was then added to 1 mL of
original solution with the concentration of 60 mg/L Cr(VI). After placing the solution
for 10 min at room temperature, the concentration of residual Cr(VI) was calculated.
Figure 4.13 shows that the treated solution with initial pH value of 2 caused a
remarkably higher reduction efficiency for Cr(VI) in contrast with that situation for the
initial pH value of 5. This manifests that some long-lived species, which we speculated
H2O2 exists in the treated solution, can recognize the reduction of Cr(VI). The reason
for reoxidation in weak acid and neutral conditions is due to the less production of
H2O2, as listed in Table 4.1, and the weaker reduction ability of H 2O2. Hence, the
strongly oxidative substance-hydroxyl radical takes an advantageous position to
reoxidize the lower oxidation states of Cr to Cr(VI). Even the content of H 2O2 is less,
the enhancement of Cr(VI) reduction in alkaline solution is obvious. It can be
–
explained that more reductive species, mainly superoxide anion (O 2 ), were generated
in the basic solution than in acidic solution [44].
Fig. 4.13 Reduction of Cr 1.2

(VI) induced by microplasma pH=2
discharge-treated water pH=5

sample with initial pH = 2
and 5 (volume of treated
0.8
water = 1 mL, volume of Cr
(VI) solution = 1 mL, [Cr
(VI)] = 60 mg/L, and
reaction time = 20 min) 0.4
0.0
0 2 4 6 8 10
Time (min)
Table 4.1 Concentration of
pH Concentration of H2O2 (mg/L)
H2O2 formed in argon
2 10.313
microplasma
discharge-reduced water 5 9.570
7 4.368
9 3.625
11 6.133
Discharge time = 2 min and volume = 25 mL
When the gas flow rate is lower than 60 mL/min, the increase in reduction
efficiency with increasing gas velocity is due to a larger reactive species generated
by the inlet gas collision with solution [17]. An intense gas stream blows away the
under surface of solution up to 80 mL/min, which will finally augment the
distance between the gas outlet and the surface of solution. As a result, it spends a
longer time to produce those reactive species that may explain the reason why
larger gas flow rates obtained the poorer reduction efficiencies. According to the
experiment results, more economic and effective value of gas flow rate that was
chosen is 60 mL/min.
Without disturbing the microplasma discharge, the action of stirring accelerates
the diffusion just by producing reactive species in Cr(VI)-containing solution,
which dramatically enhances the reduction efficiency of Cr(VI). Therefore, we
keep the solution on stirring for a better treatment result.
Microplasma discharge in a certain condition will generate a certain number of
reactive species. When the initial Cr(VI) concentration increases, more Cr(VI)
species by active particles become available for reduction and the numbers of
microplasma reducing Cr(VI) increase as well. In other words, each Cr(VI)
species in a higher concentration shares fewer reactive particles, resulting in a
lower reduction efficiency.
With an increase in input power, the energy provided by high-voltage power
supply increases, resulting in more energetic particles for Cr(VI) reduction. It can
be visually seen that intense microplasma appeared and became more and more
luminous with the increase in input power [45]. Considering work life of the
equipment and treatment efficiency, the median value of the power was finally
decided.
It is shown that an argon microplasma treatment is more efficient in reducing
Cr (VI) than an air or nitrogen microplasma. There is a little advantage of argon
due to the facts that argon discharge is easier to be triggered and more ground-
state-free radicals can be generated in the solution compared with air or nitrogen
microdis-charge with the same conditions [18]. A portion of the input energy can
be con-sumed to dissociate nitrogen when the discharge gas is air or nitrogen,
while for argon discharge the input energy is mostly dissipated to generate the
ground-state-free radicals in the solution [46]. Actually, the content of nitrate ions
produced in each situation has also been measured, and the results shown in Table
4.2 further demonstrate the given explanation. In addition, the concentration
4.4 Discussion 55
Table 4.2 Concentration of Sample −

Concentration of NO3 (mg/L)
−
NO3 in the solution after Without discharge 1.34
microplasma discharge
induced by various gases Ar 36.22
Air 210.99
N2 112.78
Discharge time = 10 min and volume = 25 mL
of H2O2 formed in the solution with argon discharge is higher than that in the case
of air and nitrogen discharge [31, 47]. Therefore, the inert gas of argon was
utilized in this study.
Cr(VI) in weak acidic solution was almost reduced when ethanol was added, which
can be explained as follows. Hydroxyl radical as one of the predominant and strongly
oxidative species can not only reoxidize the lower states of Cr but also combine
hydrogen radical with a water molecule [45]. A desirable way to reduce its impact is to
convert the hydroxyl radicals into organic radicals by the chemical reaction with
organic materials [16]. A nonpoisonous hydroxyl radical scavenger chosen for this
study is ethanol that can efficiently enhance the reduction of Cr(VI) by microdischarge
[18]. Control experiments with varying percentages of ethanol in the absence of
microdischarge treatment were carried out, and the result was presented in the inset of
Fig. 4.14. It can be observed that there was no obvious Cr(VI) reduction in ethanol
solutions without microplasma treatment, which indicated that the direct Cr(VI)
reduction was induced by microplasma, but not the additive of ethanol.
The pH value of the solution with ethanol impacts the production of sediment of Cr.
5+ 4+
Cr(III) is reported to form several hydroxyl species, such as Cr 3(OH) 4, Cr2(OH) 2,
– 0 + 2+ 0
Cr(OH) 4, Cr(OH) 3, Cr(OH) 2, and CrOH [48]. Among them, Cr(OH) 3 is the only
17
solid-state sediment. In this study, no sediment was precipitated when the ethanol
was not added to the solution, which further indicated that the presence of ethanol
plays an important role in the precipitation of Cr(III). The alcohol and Cr (VI) may
react with each other in the following way [18]:
1200 0.12
0.10
1000
0.08
I (A)
800
0.06
U (V) 600
0.04
400
0.02
200
0.0000 0.0004 0.00
0
0.0008 0.0012
T (s)
Fig. 4.14 Typical voltage and current waveforms of microplasma discharge ([Cr(VI)] = 40 mg/L,
volume = 25 mL, voltage = 1000 V, current = 40 mA, argon flow rate = 60 mL/min, and pH = 2;
the upper trace is for voltage and the bottom trace is for current)
Table 4.3 Energy efficiency of Cr(VI) reduction by microplasma discharge (MD) and other
competitive processes
Methods Conditions JCr(VI)/mg/J References
MD −4 This study
C0 = 40 mg/L, pH = 2.0, V = 25 mL, 40 W 2.0 10
−4
GDP C0 = 50 mg/L, pH = 2.0, 50 W 5.0 10 16
−4
DGD C0 = 21 mg/L, 2.0 mm hole, 150 W 0.5 10 46
−6
UV C0 = 42 mg/L, pH = 2.0, 450 W 3.9 10 50
−4
Electrolysis C0 = 50 mg/L, 1.0 A, 6.6 V 1.2 10 51
þ ð4:11Þ
CH3CH2OH þ HCrO4 þ H CH3CHOCrO3H þ H2O
In addition, 30 mg of sediment after drying was used to do the elemental

analysis and the percentage of carbon element was detected to be 2.55%.
Furthermore, the ethanol takes part in the precipitation reaction of Cr(III). In
conclusion, the ethanol not only eliminates OH but is also beneficial to remove the
chromium from aqueous solutions by generating the insoluble Cr complex.
However, the specific mechanism of ethanol in facilitating the precipitation of
chromium needs further research.
The energy efficiency of this study and of glow discharge plasma (GDP), dia-
phragm glow discharge (DGD), photocatalysis, and electrolysis are listed in Table
4.3 [49, 50]. It can be seen from Table 4.3 that the energy efficiency of Cr (VI)
reduction in microdischarge is higher than those in semiconductor photo-catalysis
and comparable to that in electrolysis and other forms of glow discharge.
Figure 4.14 shows the typical DC waveforms of voltage and current of micro-
plasma discharge. The impulsions of the voltage and current are very weak.
Hence, the energy efficiency (JCr(VI)) of Cr(VI) reduction by microdischarge in
this study can be calculated by the following equation [45]:
J ¼ 1=2C0V ð4:12Þ
Cr ð VIÞ
UIt1=2
where C0 is the initial concentration of Cr(VI) in mg/L, V is the solution volume

in L, U and I are the applied voltage in V and current in A, respectively. Also, t 1/2
is the reaction time for 50% Cr(VI) reduction efficiency in s. JCr(VI) is expressed in
mg/J.
4.5 Conclusions
The treatment of Cr(VI)-containing wastewater by microplasma discharge was

investigated. As a source of electrons and ions, microdischarges can be operated
in atmospheric pressure to initiate reduction reactions in the solution. Due to an
insoluble electrode and a smaller gas flow, this approach utilizing microplasma is
4.5 Conclusions 57
more economic than the other plasma discharges. Only a small dimension of
plasma discharge can make a big difference in water treatment. In particular, our
experi-ment is the first attempt to apply the microplasma into the treatment of
heavy metal wastewater.
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Chapter 5
Surface Sterilization by Atmospheric
Pressure Non-thermal Plasma
Abstract Surface sterilization using atmospheric pressure non-thermal plasma is rapid

and effective. In this study, the humid air gliding arc discharge was selected as the
atmospheric pressure non-thermal plasma source. It is found that inactivation rate had
reached 72.3% at the initial 0.5-min treatment and a total inactivation of the bacterial
population was achieved within only 1.5 min. The dynamic sterilization under
different air flow rates and gap distances shows that increasing air flow rates and
shorter discharge gap distance could improve sterilization efficiency. Although gap
distance also influenced treatment surface temperature, even after 1.5-min treatment at
the shortest gap distance of 1.5 cm, the surface temperature was still below 45 °C,
which is insufficient to kill bacteria via purely thermal effects. Analysis of the scanning
electron microscopic (SEM) images of bacterial cells demonstrated that the
atmospheric pressure non-thermal plasma is acting under various mechanisms driven
essentially by an oxidation effect. The experimental results show that humid air gliding
arc discharge is a promising candidate among the emerging non-thermal plasma
technology for decontamination.
Keywords Non-thermal plasma Sterilization Dynamic sterilization
5.1 Introduction
The necessity for appropriate surface disinfection and sterilization procedures has been
driven by the development of bio-compatible polymers, patient-care items, and the
constraints of industrial safety. However, some classical sterilization methods are
restricted due to safety and health problems. For example, heating or autoclave
sterilization processes are generally inapplicable for these thermal sen-sitive materials,
and fever-provoking bacterial endotoxins (pyrogens) are not removed in this process.
Ethylene oxide, considered as the mainstay of low-temperature chemical sterilization
for medical instrumentations, is highly toxic and carcinogenic, so that special
requirements are necessary to guarantee the safety of sterilization personnel. Gamma
irradiation is very effective, but it is poorly
3656-9_5
62 5 Surface Sterilization by Atmospheric Pressure Non-thermal Plasma
accepted by consumers, requires highly secured equipment, and presents a

problem similar to those of chemical treatment in that it generates a large amount
of free radicals, and the use of electron beams (beta irradiation, in other words)
has very similar limitations [1]. As for microwaves, they can be employed for
sterilization but are limited because it possibly causes thermal damage to the
processed object. Ultraviolet (UV) photon techniques can be used to sterilize, but
the sterilization occurs only when the UV photon hits are plenitudinous enough
[2]. Therefore, there is an urgent need to find more effective and economic
sterilization methods in biomedical fields and food processing [3].
Techniques commonly designated as non-thermal plasma have been emerging
in this field and are under intensive study for a number of chemical and biological
applications due to the efficient generation of radicals and reactive species [4, 5].
Several research groups have developed various plasma sources with a range of
power supply and electrode configurations and studied the efficiency of their
plasma source toward inactivation or sterilization of various microorganisms,
including bacteria, fungus, spores, and virus, and a large number of experiments
were carried out to investigate the inactivation or sterilization mechanism. The gas
gliding arc discharge is a simple and inexpensive way to generate non-thermal
plasma [6], which involves relatively high electric powers compared to other
forms of dis-charge. Therefore, gliding arc discharges have been successfully
applied in many industrial applications, such as surface treatment, emission
control of volatile organic compounds (VOCs), control of polycyclic aromatic
hydrocarbons (PAHs), inactivation of microorganisms, and wastewater treatment
[7–12]. The species present in atmospheric pressure non-thermal plasma depend
on the nature of plasma-producing medium. In the case of humid air, there are
formations of H2O2, O3, nitrate, and H2 in particular [11].
In this chapter, the humid air gliding arc discharge was selected as atmospheric
pressure non-thermal plasma source as it is simple and inexpensive. The bio-
decontamination effects of investigated non-thermal plasma were tested on the
selected bacteria (Escherichia coli), which were placed on solid agar surfaces under the
plasma effluent. Some factors affecting the inactivation efficiencies were ana-lyzed,
including the influences of air flow rates, distance between the electrodes and surfaces
of agar, and the total number of bacteria on the surfaces [12, 13].
A schematic representation of the atmospheric pressure non-thermal plasma

experimental setup is given in Fig. 5.1. The experimental apparatus consists of a
plasma generator, power supply, peristaltic pump and water supply system, and a
set of gas flow controller. As for the plasma generator, the two knife-shaped
stainless steel electrodes (95 mm long, 35 mm wide, and 4 mm thick), fixed in an
insulating bracket, are symmetrically placed on both the sides of atomizing nozzle
and connected to an AC 10-kV high-voltage transformer (50 Hz). The minimum
Fig. 5.1 Schematic H.V
representation of the
experimental setup for surface distilled air
sterilization water
peristaltic
pump electrode
distilled plasma
water zone
petri dish
gap between the electrodes is fixed at 3 mm. The air is provided by a compressed
gas cylinder (flow rate is variable), and the distilled water is provided by a peri-
staltic pump. Aerosol droplets are formed when the water meets the flowing carrier
gas. An arc is formed between the electrodes when the electrodes are applied with
a high voltage. The arc is then pushed away by the bi-phase flow from an
atomizing nozzle, and it ‘glides’ along the electrode walls until it collapses. A new
arc then forms and develops in the same way. A larger volume of non-equilibrium
plasma forms. In this way, the surfaces are treated with a short plasma exposure
time in the plasma zone.
The individual elongating plasma columns are not distinct because of the fre-
quent repetition rates of cycles of discharge. As a matter of fact, when the voltage
reaches its breakdown point, the electrical strength generates an arc at the inter-
electrode neck and the breakdown point is characterized by a very short and
intense current peak. Then, the arc is pushed down by the turbulent gas flow.
When the voltage reaches a critical value, a new dielectric breakdown occurs
within the flowing down discharge. This process is repeated several times and
ends when the critical value reaches the electrode neck breakdown voltage; then,
the discharge breaks and a new plasma arc starts again from the initial position.
Thus, a larger volume of non-equilibrium cold plasma is formed.
The isolated E. coli ATTC 25922 utilized in our experiments was purchased
from the American Type Culture Collection (Manassas, Va.). Bacteria were at first
grown in a dilute brain-heart infusion (BHI), and then the stock cultures were
deposited on LB agar slants in dark at 4 °C and prepared for inoculation before
each experiment. The E. coli stock was inoculated into sterilized LB broth and
grown overnight for 16 h at 37 °C just by shaking the stock (160 rpm). The bac-
teria that were in late stationary phase and were particularly resistant to
decontamination were chosen for our experiments [14]. The bacterial cells were
separated by centrifugation, then washed twice, and resuspended in sterilized 1.5
−1
10 M NaCl to obtain bacterial suspensions. In order to quantify the amount of
bacteria inactivation achieved by the non-thermal plasma treatment, the classical
colony counting method was used. Given volume of bacteria suspension was
plated to the LB agar and, subsequently, left the bacteria for 120 min to settle and
adhere to the agar surface. After the non-thermal plasma treatment, the plates were
incu-bated at 37 °C for 24 h in a thermostat, so that the cultures formed colonies
and untreated plates were used as the control. Each assay was carried out for three
times to calculate the mean values.
The gap distance between the electrodes and the surface of agar in Petri dish
and the flow rate of air were variable and changed as the experimental conditions
required. The discharge duration was 1.5 min, and the water flow rate was chosen
to be 0.5 mL/min in order to avoid too much of water accumulation on the surface
of the Petri dish.
5.3.1 Destruction of Bacteria by Atmospheric Pressure

Non-Thermal Plasma
The inactivation effect of humid air gliding arc discharge was tested over a period
3
of 1.5 min at a defined air flow rate (0.6 m /h) and a gap distance (3.0 cm). Figure
5.2 shows the bacterial colony on the agar plates after different treatment times (0,
0.5, and 1.5 min). It is found that most bacterial inactivation occurs in the initial
0.5-min treatment and a total inactivation of the bacterial population was achieved
within only 1.5 min. This result shows that humid air gliding arc dis-charge could
efficiently reduce the viable populations of E. coli on the surfaces of treated agar
plates.
Fig. 5.2 The bacterial samples during the surface sterilization using atmospheric pressure non-
thermal plasma
During the gliding arc discharge in air, some ultraviolet (UV) radiation and a large
amount of gas plasma were produced, which were the main components responsible
for the lethal effect. As a matter of fact, when using air as a carrier gas, and if there
exists water, the chemical active species formed in the gliding arc discharge include
−
short-lived active species (OH, NO, O, O2 , HO2, and H) and long-lived active
molecules (H2O2, O3, and other excited-state neutral molecules) [15]. The supply of
sterilized water provides sufficient water, and then, OH and NO are the main species
formed in humid air plasma during the discharge [16–18]. NO is responsible for acid
effects, and OH is the oxidizer associated with H 2O2; the two species effectively
contribute to the inactivation of bacteria together with the abovementioned actions.
The nature is also a reason that humid air gliding arc discharge was selected as the
atmospheric pressure non-thermal plasma source in experiment.
5.3.2 Influence of Air Flow Rate on the Sterilization

Efficiency
Since the air flow rate might affect the production of plasma, four sets of experi-
ments under different air flow rates were conducted. The results show that the
survival rates of E. coli under different flow rates decreased significantly with an
increase in treatment time, as shown in Fig. 5.3, which is consistent with our
previous test results. We also found that the inactivation result was most
3
prominent under the air flow rate of 1.2 m /h, with total inactivation achieved only
in 1.0-min treatment, compared to other three experiments under smaller air flow
rates that spent 1.5 min to reach complete sterilization. However, it is noted that
3
the inacti-vation efficiencies between the air flow rates of 0.6 and 0.9 m /h had a
relatively slight difference.
Fig. 5.3 The sterilization

efficiency of atmospheric 100
pressure non-thermal plasma 80 3
0.3m /h
Survival(%initial population)
under different air flow rates

3
0.6m /h
60 3
0.9m /h
3
1.2m /h
40
20
0.0 0.5 1.0 1.5

Treatment time/min
Fig. 5.4 Dynamics of the 0

sterilization efficiency using
atmospheric pressure non-
thermal plasma under
different air flow rates -1
Log10 (N/N0 )
-2 3
0.3m /h
3
0.6m /h
3
0.9m /h
-3 3
1.2m /h
y=0.1611-1.2255x (r=0.9753)
y=0.0649-1.4984x (r=0.9975)
y=0.0050-0.8163x (r=0.9995)
-4 y=-0.1534-2.3238x (r=-0.9708)
0.0 .5 1.0 1.5

Treatment time/min
To further understand the influence of air flow rate on sterilization efficiency,

the inactivation kinetics in the treatment of atmospheric pressure non-thermal
plasma was analyzed and the corresponding line plots were obtained, as illustrated
in Fig. 5.4, which show that the dynamic inactivation process suitably correlate
with the first-order kinetic equation.
Through this analysis, it is concluded that the air flow rate has certain influence
on the sterilization efficiency of non-thermal plasma and that the improved inac-
tivation effect of larger flow rate can be attributed as a rapid accumulation of
active particles on the agar surfaces, thus raising the reaction rate of plasma with
agar surfaces. Nevertheless, larger flow rate requires higher level of air supply
system and higher consumption of energy. Consequently, in practical applications,
we should choose a proper air flow rate considering both the sterilization
efficiency and the specific application requirements.
5.3.3 Influence of Gap Distance Between Agar Surfaces

and Electrodes on the Sterilization Efficiency
The gap distance is also an important parameter in this study, and a series of
experiments based on atmospheric pressure non-thermal plasma were carried out
to investigate the influence of gap distance between agar surfaces and electrodes
on the sterilization efficiency. The results are illustrated in Fig. 5.5 and show that
bacteria survival rate increases with reducing gap distance and mostly bacterial
inactivation occurs in the first 30 s.
For more in-depth information, the experimental data of the surface sterilization
efficiency of atmospheric pressure non-thermal plasma under different gap distances
utilizing mathematic models were calculated again, showing the perfect relevance
Fig. 5.5 The surface

sterilization efficiency of 100 1.5cm
atmospheric pressure non- 3.0cm
Survival(%initial population)
thermal plasma under 80 4.5cm
different gap distances 6.0cm
60
40
20
0.0 0.5 1.0 1.5

Treatment time/min
0.0
Fig. 5.6 The dynamics of

surface using atmospheric
-.5
pressure non-thermal plasma
under different gap distances
)
-1.0
Log 10 (N/N 0
-1.5 1.5cm
3.0cm
-2.0 4.5cm
6.0cm
y=0.1519-1.5939x (r=0.9753)
-2.5 y=0.1084-0.9943x (r=0.9561)
y=-0.0016-0.4875x r=0.9999)
y=0.0053-0.2094x (r=0.9937)
-3.0
0.0 .5 1.0 1.5

Treatment time/min
of dynamic inactivation process to the first-order kinetic equation. The details are
shown in Fig. 5.6. These results also illustrated that sterilization efficiency can be
improved by diminishing the gap distance.
5.3.4 Temperature Variations of Surface Sterilization

Efficiency Under Different Contact Distances
Considering that the discharge gap will affect the surface sterilization efficiency, as
demonstrated previously, the changes in temperature during discharge process were
Fig. 5.7 The temperature 45

variations of surface
sterilization efficiency using
atmospheric pressure non- 40
thermal plasma under
different gap distances
35
30 1.5cm
3.0cm
25 4.5cm
6.0cm
20
0.0 0.5 1.0 1.5

Treatmen time (min)
monitored using infrared detection gun to further understand the mechanism of

bacteria inactivation by the atmospheric pressure non-thermal plasma. From the
results shown in Fig. 5.7, we can find that the surface temperature increased as the
gap distance became smaller. However, the highest temperature after 1.5 min of
plasma exposure was only 41.8 °C, which is still not sufficient for melting agar
and inactivating E. coli via purely thermal effects. The relatively low temperature
might be accounted for the atomized water spray by the action of air flow, which
provided water that is used to produce plasma and at the same time played an
important role in cooling.
5.3.5 Influence of the Total Number of Bacteria in

the Surface on the Sterilization Efficiency
In order to investigate the influences of the total number of bacteria on the surface
sterilization using non-thermal plasma, we conducted comparative experiments
with the total number of bacteria of different order of magnitude, which were n 10
2 3
(about 80), n 10 (about 600), and n 10 (about 1500). From the test results
summarized in Fig. 5.8, it can be seen that when the total number of bacteria was
3
n 10 , live bacteria can still be detected after the 1.5-min treatment because all cell
layers be incapable of penetration by discharge plasma. However, the dif-ference
among the total number of various bacteria was generally insignificant, which
might be attributed to the fairly good sterilization effect when agar surfaces were
rather close to the electrodes. In other words, the effect of the total number of
bacteria on the sterilization efficiency is not dominant if proper parameters have
been chosen to produce plasma.
Fig. 5.8 Influences of the
population)
total number of bacteria on 100
the surface sterilization using 80 n x103 CFU/mL
atmospheric pressure non-
thermal plasma n x10 CFU/mL
n x102 CFU/mL
Survival(%initial
60
40
20
0.0 0.5 1.0 1.5
Treatment time/min
5.3.6 Scanning Electron Microscopic Photomicrographs

of E. Coli in the Treatment
After the plasma treatment, the agar surface was wiped gently to transfer the
remaining bacteria to the sterile cotton. Afterward, the sterile cotton was immersed
in sterile distilled water and then washed repeatedly to make bacteria scatter in
distilled water. Then, the distilled water containing E. coli cells was centrifuged
and the relevant supernatant was removed. In order to prevent any destruction
after sampling, the E. coli cells were fixed with 2.5% glutaraldehyde for 6 h. Then,
the cultures were centrifuged (20 °C, 5000 g, 10 min) and the relevant supernatant
was removed. The corpuscles were rinsed thrice in PBS buffer (0.8% NaCl, 0.02%
KCl, 0.17% Na2HPO4, and 0.8% KH2PO4) and dehydrated by successive treat-
ments of ethanol in water, in which the ethanol concentration for each treatment
was increased steadily (from 30 to 100%). Later, the samples were treated by
anhydrous tert-Butyl alcohol for three times and finally dried at a critical temper-
ature. Then, all the samples were coated with gold powder in a sputter coater and
examined by a scanning electron microscope (SEM, S-520; Hitachi, Japan).
Scanning electron microscopic observations of the bacteria submitted to atmo-
spheric pressure non-thermal plasma indicate that the cell morphology of the
microorganism is significantly affected (Fig. 5.9). Figure 5.9a represents the E.
coli samples before discharge treatment, in which the cell membrane is smooth
and the morphology is fairly complete. However, after 0.5-min treatment, it can be
seen that E. coli cells are somehow deformed and the cell surfaces become rough
(Fig. 5.9b). In addition, E. coli cells suffered dramatic morphological changes
after 1.5 min exposed to the plasma treatment (Fig. 5.9c).
Fig. 5.9 The SEM images of the bacteria cells during the surface sterilization using atmospheric
pressure non-thermal plasma
5.3.7 Mechanism of Bacteria Inactivation by Non-thermal

Plasma
The synergistic effects that took place in the atmospheric pressure non-thermal
plasma system are summarized [19]. Many damages can be done to biomacro-
molecule by atmospheric pressure non-thermal plasma, but the dominating
damage that leads to death is not always very clear.
The UV radiations have been proposed as the main component of bactericidal
agents during the discharge, since it is related to the irreparable damages of DNA
and RNA [20]. Biological impact of UV radiations is primarily due to the
absorption of photons by nucleic acids. In bacteria, various repair mechanisms are
generally quite efficient and rapid [21], indicating that cell death occurs only when
the UV photon hits are plenitudinous enough that the bacterial repair mechanism
cannot manage [2]. Although bacteria cells were grown in the agar medium below
the electrodes that would be affected by the UV radiations to some extent, the
number of UV photons generated in the discharge is limited [22], so the corre-
sponding lethal doses are not delivered and the sterilization effect observed with
non-thermal plasma probably involves other factors.
Ozone is a powerful oxidizing agent that forms when the carrier gas contains
oxygen. The gaseous ozone can react with the fatty acids and peptides of the cell
wall [23], stimulate the lipid peroxidation [24], and result in single-strand DNA
breaks [25], which eventually lead to extensive DNA damage and death. Bacterial
inactivation by ozone is a function of ozone concentration per viable bacteria.
However, water vapor in the air–water medium can absorb a substantial part of
the electronic energy of the discharge that could otherwise be used in the ozone
for-mation process [26], which indicates that the production of gaseous ozone is
below the threshold concentration ozone that can inactivate bacteria.
Consequently, the chemical processes of oxidation and acidification occurring
during the discharge are proposed to be the main mechanisms to explain the
inactivation of bacteria. A spectroscopic investigation of the atmospheric
pressure non-thermal plasma revealed that the radicals such as NO and OH were
the main
species formed in the non-thermal phase [18]. It is demonstrated that NO is

responsible for acid effects and for a steep lowering of the pH of the medium,
since it can lead to the formation of HNO 2 and HNO3 [2]. The other radical OH,
which was produced in high quantities, is responsible for a strong oxidizing effect
[18, 27], having extremely high-rate constants for reactions with almost every
type of molecule found in living cells [28], and significantly damages most of the
bio-logical molecules. Additionally, H2O2 formed in the aqueous medium is also
an oxidizing agent that has a very high sterilization activity, which can damage the
DNA and result in the death of cells [29].
Although there is no participation of high electric field or thermal effect, all
these abovementioned factors coming together in bacteria inactivation by
atmospheric pressure non-thermal plasma source are already capable of producing
rapid and effective sterilization effect.
5.4 Conclusions
The humid air gliding arc discharge is a rapid and effective atmospheric pressure non-
thermal plasma source. Experimental results showed that air flow rate influ-enced
sterilization efficiency to some extent. The total bacteria number plays a vital role in
sterilization efficiency as well, but very limited. The gap distance between agar
surfaces and electrodes has an impact on surface temperature and the inacti-vation
performance of the reactor, but the obtained surface temperature is insuffi-cient to kill
bacteria. It is also concluded that inactivation mechanisms using the atmospheric
pressure non-thermal plasma is driven essentially by an oxidation effect. However,
further research work is still needed to understand much better the mechanisms of
bactericidal reduction and to optimize the sterilization process. Additionally, the
combination of the atmospheric pressure non-thermal plasma and other catalysts that
possesses great research potentiality is also in our agenda.
References
1. Moreau M, Orange N, Feuilloley MGJ. Non-thermal plasma technologies: new tools for bio-
decontamination. Biotechnol Adv. 2008;26(6):610–7.
2. Chen FN, Yang XD, Wu Q. Photocatalytic oxidation of Escherischia coli, Aspergillus niger,
and formaldehyde under different ultraviolet irradiation conditions. Environ Sci Technol.
2009;43(12):4606–11.
3. Burlica R, Grim RG, Shih KY, Balkwill D, Locke BR. Bacteria inactivation using low power
pulsed gliding arc discharges with water spray. Plasma Process Polym. 2010;7(8):640–9.
4. Bruggeman P, Leys C. Non-thermal plasmas in and in contact with liquids. J Phys D Appl
Phys. 2009;42(5):053001 (28 pp).
5. Brisset JL, Moussa D, Doubla A, Hnatiuc E, Hnatiuc B, Youbi GK, Herry JM, Naitali M,
Bellon-Fontaine MN. Chemical reactivity of discharges and temporal post–discharges in
plasma treatment of aqueous media: examples of gliding discharge treated solutions. Ind
Eng Chem Res. 2008;47(16):5761–81.
6. Lesueur H, Czernichowski A. Device for generating low-temperature plasmas by formation
of sliding electric discharges. Patent FR2639172. 1990.
7. Czernichowski A. Gliding arc applications to engineering and environment control. Pure
Appl Chem. 1994;66(6):1301–10.
8. Krawczyk K, Ulejczyk B. Decomposition of chloromethanes in gliding discharges. Plasma
Chem Plasma P. 2003; 23(2):265–81.
9. Ferenc Z, Wandrasz JW. Use of GLIDARC reactor for decomposition of toluene vapours in
hot exhausts. High Temp Mater P. 2004; 8(1):31–7.
10. Du CM, Wang J, Zhang L, Li HX, Liu H, Xiong Y. The application of a non–thermal plasma
generated by gas–liquid gliding arc discharge in sterilization. New J Phys. 2012; 14:013010
(16 pp).
11. Yan JH, Du CM, Li XD, Sun XD, Ni MJ, Cen KF. Plasma chemical degradation of phenol in
solution by gas–water gliding arc discharge. Plasma Sources Sci Technol. 2005;14(4):637–44.
12. Wang J. Basic research on the inactivation of bacterium by plasma generated by gliding arc
discharge. Yat–sen University. 2011.
13. Du CM. Non-thermal arc plasma technology and application. Beijing: Chemical Industry
Press; 2015.
14. Ponniah G, Chen H, Michielutti R, Salonen N, Blum P. Single-cell protein profiling of
wastewater enterobacterial communities predicts disinfection efficiency. Appl Environ
Microb. 2003;69(7):4227–35.
15. Kamgang-Youbi G, Herry JM, Meylheuc T, Brisset JL, Bellon-Fontaine MN, Doubla A.
Microbial inactivation using plasma-activated water obtained by gliding electric discharges.
Lett Appl Microbiol. 2009;48(1):13–8.
16. Benstaali B, Moussa D, Sauvage L, Addou A, Cheron BG, Brisset JL, editors. Interaction
between plasma and aqueous solutes. In: The Proceedings of the International Symposium
on High Pressure, Low Temperature Plasma Chemistry, Hakone VI, Cork, Ireland. 1998.
17. Benstaali B, Moussa D, Addou A, Brisset JL. Plasma treatment of aqueous solutes: some
chemical properties of gliding arc in humid air. Eur Phys J-Appl Phys. 1998;4(2):171–9.
18. Laroussi M, Leipold F. Evaluation of the roles of reactive species, heat, and UV radiation in
the inactivation of bacterial cells by air plasmas at atmospheric pressure. Int J Mass
Spectrom. 2004;233(1–3):81–6.
19. Moussa D, Naitali M, Herry JM, Hnatiuc B, Brisset JL. Reactions induced by electrical
discharges in pollutant abatement and bacterial inactivation. 12th International Conference
on Optimization of Electrical and Electronic Equipment; 2010. p. 1329–1335.
20. Lerouge S, Wertheimer MR, Marchand R, Tabrizian M, Yahia L. Effect of gas composition
on spore mortality and etching during low-pressure plasma sterilization. J Biomed Mater
Res. 2000;51(1):128–35.
21. Gaunt LF, Beggs CB, Georghiou GE. Bactericidal action of the reactive species produced by
gas–discharge nonthermal plasma at atmospheric pressure: A review. Ieee T Plasma Sci.
2006;34(4):1257–69.
22. Moreau M, Feuilloley MGJ, Orange N, Brisset JL. Lethal effect of the gliding arc
discharges on Erwinia spp. J Appl Microbiol. 2005;98(5):1039–46.
23. Doroszkiewicz W, Sikorska I, Jankowski S. Studies on the influence of ozone on
complement–mediated killing of bacteria. FEMS Immunol Med Mic. 1994;9(4):281–5.
24. Gardner CR, Robson EA, Stanford C. The presence of monoamines in the nervous system of
Peripatopsis (Onychophora). Experientia. 1978;34(12):1577–8.
25. Ishizaki K, Sawadaishi K, Miura K, Shinriki N. Effect of ozone on plasmid DNA of
Escherichia coli in situ. Water Res. 1987;21(7):823–7.
26. Du CM, Sun YW, Zhuang XF. The effects of gas composition on active species and
byproducts formation in gas-water gliding arc discharge. Plasma Chem Plasma P. 2008;28
(4):523–533.
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27. Benstaali B, Boubert P, Cheron BG, Addou A, Brisset JL. Density and rotational
temperature measurements of the OH degrees and NO degrees radicals produced by a
gliding arc in humid air. Plasma Chem Plasma P. 2002;22(4):553–71.
28. Halliwell B, Gutteridge JMC. The importance of free radicals and catalytic metal ions in
human diseases. Mol Aspects Med. 1985;8(2):89–193.
29. Talaro. KP, Chess. B. Foundations in microbiology: basic principles. New York: McGraw-
Hill; 2002.
Chapter 6
Removal of Volatile Organic Compounds
Using Plasma Fluidized Bed
Abstract Recently, hazardous contamination of volatile organic compounds

(VOCs) in the environment is the current study area that has attracted more
number of research scholars. To remove VOCs, non-thermal arc plasma fluidized
bed is considered one of the best techniques. In this chapter, the research status of
non-thermal arc plasma fluidized bed for the abatement of VOCs that polluted the
gas flow is elucidated. Plasma fluidized bed is simple to construct and operate and
does not produce any by-products. It manages the organic wastes with higher
efficiency, processing especially for the low concentration winds. It is a promising
technology and has broad application prospects.
Keywords Plasma fluidized bed Volatile organic compounds Removal
6.1 Introduction
Volatile organic compounds (VOCs) are generally defined as either organic com-
pounds with a vapor pressure larger than 0.1 mm Hg in room temperature and
atmosphere pressure or organic compounds with a boiling point lower than 150 °C.
There are various kinds of VOCs, which reach around 1 million and are still growing
rapidly. According to the differences of composition and characteristics, VOCs can be
divided into five groups as follows: (1) hydrocarbon, including alkanes (except
methane), olefins, and aromatics; (2) oxygenated organic com-pounds, such as
aldehydes, alcohols, ketones, and esters; (3) nitrogenous organic compounds, such as
amine, amide, and acrylic; (4) halogenous organic compounds, including
halohydrocarbon chloride; and (5) sulfur-containing organic compounds, including
mercaptan, sulfide, thiourea, thiophenol, and carbon disulfide. Some organic
compounds, such as hydrocarbons, nitrogenous organic compounds, halogenous
organic compounds, and sulfur-containing organic compounds, can release unpleasant
smell. Due to the developments in science, industry, and
3656-9_6
76 6 Removal of Volatile Organic Compounds …
transportation, as well as the increase in urban population, VOCs have become

increasingly outstanding, thus demanding the development of a new technology
urgently [1].
6.2 Removal of Volatile Organic Compounds Using

Plasma Fluidized Bed with Catalysis
6.2.1 Experimental Section
The schematic diagram of the experimental setup is shown in Fig. 6.1. The plasma
setup consists of the plasma fluidized bed and high voltage supply. The plasma
fluidized bed comprises the gas inlet, quartz vessel, tetrafluoroethylene base,
knife-shaped stainless steel electrodes, conical stainless steel mesh, c-Al2O3 cata-
lyst particles containing precious metal such as Pd and Pt as active components,
quartz cover, and gas outlet. In this reactor, the quartz vessel and quartz cover are
connected to form a cavity and the tetrafluoroethylene base is equipped as the
Fig. 6.1 Schematic diagram of plasma fluidized bed for treating organic waste gas
6.2 Removal of Volatile Organic Compounds … 77
bottom of the quartz vessel. At least two knife-shaped stainless steel electrodes are
fixed at the tetrafluoroethylene base and connected with high voltage power supply
through wire. The gas inlet is located at the center of the tetrafluoroethylene base.
Conical stainless steel mesh is located at the center and fixed directly above the
electrodes and on the top of the quartz vessel. Inside the stainless steel are the c-
Al2O3 catalyst particles.
The degradation process of VOCs in plasma fluidized bed happens in the fol-
lowing procedures. Exhausted gas enters the plasma reactor through the gas inlet.
High voltage power supply is connected with knife-shaped electrodes. Breakdown
discharge begins in the smallest gaps between the electrodes, and then exhausted
gas forces the discharge along the surface of the electrodes, by which the non-
thermal plasma is generated. In this way, a large number of charged particles,
excited species, radicals, electrons, and photons are generated. The activated gas
passes through the stainless mesh, and the c-Al2O3 catalyst can be forced to move
like a fluid that act as plasma fluidized bed. In the plasma fluidized bed, the
activated gas can effectively activate the catalyst by diffusion, absorption, migra-
tion, and bombardment. In this way, the catalyst is polarized and secondary elec-
trons can be generated, thus forming an enhanced electric field on the surface. On
the other hand, catalyst can absorb some VOCs and form an enriched area. Hence,
VOCs can be effectively degraded and completely mineralized to inorganics by
the plasma coupled with the catalyst reaction. Clean gas exists in the reactor
through the gas outlet.
Plasma fluidized bed integrates plasma technology with catalyst reaction and
effectively fulfills the abatement of VOCs, especially for treating the exhausted
gas with a small flow rate and large concentration of pollutants. Furthermore, this
type of reactor can become a movable system by installing it on a truck.
6.2.2 Results
In this experiment, toluene is selected as the model of the VOCs for treatment. The
3 3
initial concentration is set as 13,000 mg/m , with a flow rate of 10 m /h. The discharge
voltage is set as 10 kV. Exhausted gas to be treated is introduced into plasma device
through a gas inlet, and then, the power supply connected with the electrodes is started
and the output voltage is adjusted to 10 kV. Then, the breakdown discharge occurred at
the smallest gap between two electrodes (length 165 mm and thickness 3 mm) and
forced down along the surface of the electrodes by the flowing gas. During the moving
of breakdown discharge, a large number of active species (charged species, excited
species, radicals, electrons, and photos) are generated. Activated gas surpassed the
stainless mesh and was then forced through c-Al2O3 catalyst loaded with Pd and Pt
that act as plasma fluidized bed. In the plasma fluidized bed, activated gas can
effectively activate the catalyst by diffusion, absorption, migration, and bombardment.
In this way, the catalyst is polarized and secondary electrons can be generated, thus
forming an enhanced electric field on the
78 6 Removal of Volatile Organic Compounds …
surface. On the other hand, catalyst can absorb some VOCs and form an enriched
zone. Hence, toluene can be effectively degraded and mineralized to inorganics by
the plasma coupled with the catalyst reaction. In this reactor, degradation
efficiency can be achieved up to 88%. After degradation, clean gas exists in the
reactor through the gas outlet.
6.3 Removal of Volatile Organic Compounds Using

Plasma Fluidized Bed with Activated Carbon
6.3.1 Experimental Section
The schematic diagram of the experimental setup was similar to the one shown in
Fig. 6.1. Particle-activated carbon is used to replace the c-Al2O3 catalyst. Using
this reactor for treating the VOCs containing gas flow, organic-polluted gas to be
treated is introduced into the plasma device through a gas inlet and the power
supply connected with electrodes is started. Then, the breakdown discharge
occurred at the smallest gap between two electrodes (length 165 mm and thickness
3 mm) and forced down along the surface of the electrodes by the flowing gas.
During the moving of breakdown discharge, non-thermal arc plasma is generated
and a large number of active species (charged species, excited species, radicals,
electrons, and photos) are generated. This activated gas species can lead to the
conversion of the VOCs into CO2, CO, and H2O and other small molecules. The
resident benzene and intermediates pass through the stainless mesh with flowing
gas. Then, the activated carbon particles (column coal active carbon: diameter 6.0
mm and length 100– 150 mm) move into fluidization, which acts as plasma
fluidized bed. Activated carbon can absorb the residue VOCs and the intermediates
and then form an enriched area of the toxics. On the other hand, activated gas can
effectively activate the activated carbon by diffusion, absorption, migration, and
bombardment, which can simultaneously degrade and mineralize. Hence,
activated carbon can be mod-ified and regenerated. Therefore, the abatement of
VOCs can be effectively realized by the plasma coupled with the activated carbon.
The clean gas leaves the reactor through the gas outlet.
6.3.2 Results
In this experiment, benzene is selected as the model of the VOCs for treatment. The
initial concentration is set as 15,000 mg/m3, with a flow rate of 13 m3/h. The
discharge voltage is set as 10 kV. Exhausted gas to be treated is introduced into
the plasma device through a gas inlet, and then, the high voltage power supply
con-nected with electrodes is started and the output voltage is adjusted to 10 kV.
Then, the breakdown voltage occurred at the smallest gap between two
electrodes (length
6.3 Removal of Volatile Organic Compounds … 79
165 mm and thickness 3 mm) and forced down along the surface of the electrodes by
the flowing gas. During the moving of breakdown discharge, non-thermal arc plasma
is generated and a large number of activated species (charged species, excited species,
radicals, electrons, and photos) are generated. This activated gas species can lead to
the conversion of the VOCs into CO 2, CO, and H2O and other small molecules. The
resident benzene and intermediates pass through the stainless mesh with flowing gas.
Then, the activated carbon particles (column coal active carbon: diameter 6.0 mm and
length 100–150 mm) move into fluidization, which acts as the plasma fluidized bed.
Activated carbon can absorb the residue VOCs and the intermediates and then form an
enriched area of the toxics. On the other hand, activated gas can effectively activate
the activated carbon by diffusion, absorption, migration, and bombardment, which can
simultaneously be degraded and miner-alized. Hence, activated carbon can be
modified and regenerated. Therefore, the abatement of VOCs can be effectively
realized by the plasma coupled with the activated carbon, and degradation efficiency
can be achieved up to 95%.
Reference
1. Du CM. Degradation of organic contaminations from gas and liquid phase using gliding arc
discharge plasma. Hangzhou: Zhejiang University; 2006.

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Advanced Topics in Science and Technology in China

More information about this series at http://www.springer.com/series/7887

ISSN 1995-6819 ISSN 1995-6827 (electronic)

Library of Congress Control Number: 2017930407

Printed on acid-free paper

This Springer imprint is published by Springer Nature

Guangzhou, China ChangMing Du

1 Application of Plasma Technology for Remediating

3.3.1 Plasma Discoloration and Degradation of Single Dye . . . . . 24

5.3.5 Influence of the Total Number of Bacteria

Abstract The non-thermal plasma-related classifications and the basic principles of

Keywords Non-thermal plasma Plasma technology Pollution treatment

Nowadays, the methodologies being followed in the production and

1.2 Plasma Generation and Application

1.3 Plasma Technology in Environmental Protection

Fig. 1.1 Schematic

• Organic wastewater treatment;

Keywords Plasma Fluidized bed Contaminated soil Phenanthrene Remediation

2.2 Experimental Section

2.2.1 Experimental Setup

The schematic representation of the experimental setup for remediating PAH-

Fig. 2.1 Schematic diagram of the experimental setup

analysis section. The plasma reactor was connected to a high-voltage AC power

2.2.2 Materials and Analyses

Phenanthrene and other standards used were purchased from Sigma-Aldrich

The mineralization of PHE was measured by a total organic carbon analyzer

The exhaust-gas ozone concentration is measured by the indigo dye reaction.

2.3 Results and Discussions

2.3.1 Effect of the Solid Bed Location

Fig. 2.2 Effect of location of 100

2.3.2 Effect of the Input Energy Density

Fig. 2.3 Effect of the energy 6.0x10-5

density on the PHE

the energy efficiency (air flow 80

Energy density (J/g soil)

2.3.3 Effect of the Flow Rate of the Carrier Gas

Fig. 2.4 Effect of air flow on

Fig. 2.5 Effect of the flow

flow rate=10 L/min

Treatment time (min)

In addition, a similar energy variation of efficiency as function of the flow rate

2.3.4 Effect of the Soil Moisture Content

Fig. 2.6 Effect of soil 100

Treatment time (min)

O þ H2O ! H2O2 ð2:7Þ

O þ H2O ! 2OH ð2:8Þ

2.3.5 Role of Active Species

Fig. 2.7 Effect of adding OH 100

degradation (energy density = 1 mL ethanol

Treatment time (min)

2.3.6 TOC Analysis

2.3.7 Proposed Pathway of the PHE Degradation

Fig. 2.8 TOC removal 70

Table 2.1 Compounds identified in the products

Fig. 2.9 Possible pathway of the degradation of phenanthrene by the PFB

In the present study, the remediation of PHE-contaminated soil by a novel plasma

9. Wang TC, Lu N, Li J, Wu Y. Evaluation of the potential of pentachlorophenol degradation in

Abstract Degradation and discoloration of three kinds of representative textile dyes

Keywords Gliding arc discharge Plasma Dyes wastewater Degradation

The large quantity of wastewater produced by textile industry is characterized by

to the environment [2]. Currently, the conventional treatments, such as biodegra-

3.2 Experimental Section

3.2.1 Plasma Apparatus