Locke 194

Environmental Applications of Electrical Discharge Plasma with Liquid Water

-- A Mini Review --

Bruce R. Locke
Florida State University, Department of Chemical and Biomedical Engineering,
FAMU-FSU College of Engineering, Tallahassee, Florida, USA

I. INTRODUCTION and the gas-liquid contacting patterns. In addition, to the

energy efficiency other factors include cost and complex-
Electrical discharge plasmas that contact liquids, in-
ity of the power supplies, durability and properties of
cluding both aqueous and organic fluids, have garnered
electrode materials, and possible requirements for carrier
much recent interest because they lead to complex and
gases or other chemicals. As in all chemical reaction-
interesting scientific problems and engineering challeng-
based treatment technologies the formation of reaction
es and there are a number of important applications.
products must be carefully considered. Another im-
While an early report of plasma contacting liquids is over
portant factor is the power supply cost and the efficiency
120 years old[1], significant efforts in plasma-induced
of conversion of the input power into discharge power.
electrolysis were initiated in the 1950’s[2-5], and more
Full economic and technical evaluations with compari-
recent lines of research on water treatment and environ-
sons to competitive techniques such as the wide range of
mental applications started approximately 25 years
advanced oxidation methods available have not yet been
ago[6]. In parallel, analysis of electrical breakdown in
published. It is always important to determine what
dielectric liquids is important in high voltage power
unique aspects and/or improvements in process efficien-
transmission and corrosion. During the last two decades
cy the plasma can provide compared to conventional
a wide range of different types of power sources (AC,
technologies. However, recently pilot scale plants have
DC, pulsed, microwave, and radio frequency) with many
been developed for water treatment (ballast water and
different and very creative means to configure the elec-
chemical agent destruction) and air cleaning[10-14].
trodes and to contact the plasma with the liquids have
Many reviews of the basic principles and applications
been developed and studied. To further enhance effi-
of plasma with liquids and plasma in environmental pol-
ciency, combinations of plasma with heterogeneous and
lution control have been published during the last ap-
homogeneous catalysts and adsorbents have been inves-
proximately ten years[7, 8, 10, 15-22]. These reviews
tigated. In light of all of this work the field of plasma
provide good coverage of the basic chemistry, physics,
contacting liquids can no longer be considered “new” or
and engineering advances in the field and should be con-
“novel”. However, due to the complexity of the issues
sulted for detailed analysis of these topics. The goals of
spanning plasma chemistry, plasma physics, and electri-
the rather general present review are to 1) direct the re-
cal and chemical engineering there remain many chal-
searcher to the appropriate literature summarizing ad-
lenges to the successful application of such technology.
vances in the field, 2) highlight where additional tech-
The two main environmental applications areas are in
nical developments are needed for application to pollu-
water and air (using “wet-plasmas”) pollution treatment,
tion control, and 3) provide some commentary on where
and there is also interest in applying plasma to ground-
major efforts should be directed. The aim here is not to
water and soil treatment. While there are many potential
provide a comprehensive review of all the literature, but
applications in water and air treatment, commercial ap-
to assist researchers in selecting important topics for fur-
plications are still under development.
ther research.
One of the most important factors affecting the prac-
tical use of plasma discharge for processing of moderate
to large scale quantities of liquids is the operating energy
costs. Energy yields for the production of various chem- II. APPLICATIONS
icals (H2, H2O2, ·OH) and the destruction of compounds
Very broadly, applications of plasma processes to
and microorganisms in water have been reviewed and
pollution control can be classified into direct and indirect
summarized[7-9]. The efficient generation of active
processes. For example, the most important indirect ap-
chemical species, including reactive oxygen (O3, ·OH, O,
plication of a plasma process in pollution control is the
H2O2), and in some cases, particularly for microbe inac-
use of dielectric barrier discharges (DBD) for ozone gen-
tivation, reactive nitrogen species (ROS), depend strong-
eration from dry gases, preferably pure oxygen; gas
ly on the type of electrical discharge, the energy input,
streams containing ozone are thereafter injected into wa-
ter for chemical oxidation of harmful pollutants, usually
Corresponding author: Bruce R. Locke organic compounds and sometimes bacteria or other bio-
e-mail address: [email protected] logical species, and in applications to gas cleaning, for
example, ozone is injected into gas streams for oxidation
195 International Journal of Plasma Environmental Science & Technology, Vol.6, No.3, DECEMBER 2012

of nitrogen oxides and for diesel particulate filter clean- liquid films or water droplets are the most efficient[8-9,
ing[23-28]. Another indirect application of plasma is in 49]. The major reason for this is that the generation of
the generation of UV light[29] used in photochemical gas phase plasma requires much less energy than that
and photocatalytic processes. Commercial scale reactors needed to generate plasma directly in the liquid phase. In
for the generation of ozone have been highly optimized a liquid, thermal energy is generally needed to create
and studied for many years[30-33] and the chemistry of microbubbles or local inhomogeneities where the dis-
ozone in water is well understood and established[34, 35]. charge can form[50-53] and larger electric fields are re-
On the other hand, direct application of plasma to a quired for breakdown[15]. In addition, some of the ener-
contaminated liquid or gas/liquid system has been the gy is converted into mechanical factors, including high
subject of a very large range of experimental studies[7, 8, pressure and sometimes shockwaves (see for [54] re-
15-19]. It is very important for researchers working on view). (However, it can be noted that recent sub-
direct plasma processes to understand and take into ac- nanosecond discharges directly in the liquid may change
count the gas phase chemistry of ozone generation and this conclusion, but no chemical yield data has yet been
the liquid phase chemistry of ozone oxidation in order to reported for such discharges[55].) In addition, in the
assess how the direct application improves or differs case of thin films and droplets of water the reactants
from the indirect application of the plasma. For example, formed in the gas or at the gas-liquid interface high rates
it is well known that the presence of water vapor reduces of mass transfer between the gas and liquid can be sus-
the formation of ozone in gas phase plasma[36] and tained due to the large gas-liquid interfacial surface area.
therefore reduction in the formation of ozone by water Applications of other reactor designs besides the water
vapor should be compensated by an increase in the for- spray and falling film may be important to cases in mate-
mation of some other factor or species (i.e., ·OH) that rials and biomedical engineering where energy costs are
enhances degradation reactions. Since the direct for- not as important. However, where energy costs are the
mation of ozone from dry gases is generally very effi- limiting factor the gas-liquid film and droplet reactors are
cient, any application that couples the plasma to the liq- most likely to be the best alternative regarding the plas-
uid phase must demonstrate improvements in process and ma for processing large volumes of gases and liquids. It
chemical efficiencies beyond those due directly to ozone is strongly recommended that researches conduct more
reactions. This is usually a very difficult endeavor and it studies with these types of reactors for environmental
requires careful control experiments as well as accurate applications where moderate to large volumes of gases
mathematical models. Determining reaction pathways is and liquids need to be treated and processed.
very difficult even in indirect applications where ozone Most energy yields for organic compound degrada-
can lead to other reactive pathways, e.g. ·OH, depending tion by direct plasma generally span the range from 10-10
upon the solution conditions (i.e., pH). Further compli- to 10-8 mol/J and the highest energy yield for degradation
cations arise, for example, because the reactions of ozone of an organic compound dissolved in aqueous solutions
and ·OH with the target organic (e.g., phenol) can be by plasma processes is 4x10-7 mol/J for decoloration of
strongly affected by the distribution of reaction degrada- the dye indigo carmine by pulsed corona discharge with
tion products[37]. water spray reactor[56]. (Values as low as 10-12 mol/J for
Other applications, not specifically related to envi- pentachlorophenol in glow discharge have also been re-
ronmental issues, of plasma in contact with liquids that ported[57]; this result reflects the low reactivity of this
are not directly related to pollution control include chem- compound with ·OH.) Table I shows example cases for
ical synthesis (e.g., H2[38], H2O2[9], nitrogen oxides), some of the highest energy yields summarized in the re-
biomedicine (wound healing, cancer treatment, disinfec- cent review[8]. In all cases, clearly the existence and
tion[39-45]) and materials synthesis (nano-particles from composition of the gas phase was very important in in-
organic liquids[46, 47]). While this review does not fo- creasing the energy yield, and typically, the addition of
cus on these other aspects, some of the general comments oxygen enhances the oxidation reactions through for-
given below will apply to these other applications. mation of O3, various oxygen radicals, and ·OH. Despite
the wide range of reactor types and configurations, gas
composition, liquid composition and other conditions
III. CHEMICAL REACTORS AND EFFICIENCIES (pH and conductivity), energy yields higher than 4x10-7
mol/J have not been reported for direct plasma processes.
The type of power delivery mode (AC, DC, pulsed, This limit (2.5x103 kJ/mol) is approximately 5 to 10
MW, and RF) for generating plasma inside or in contact times higher than typical bond energies of organic com-
with a liquid phase is closely connected to the type of pounds (C-H: 413, C-C: 348, C=C: 614, and C-O: 360
electrode used (including the electrode geometry) and to kJ/mol).
the phase distribution of the gas and liquid (placement of For comparison, in the case of phenol the energy
electrodes in gas or in liquid). Reviews of various gas costs for oxidation by ozone (indirect plasma) are in the
phase reactors[48] and various gas-liquid phase reactors range 10-8 to 10-6 mol/J and by the non-plasma based
can be consulted for details[8, 9, 19, 49]. In general, for Fenton method (H2O2 + Fe) the costs are 10-7 mol/J[58,
chemical process efficiency in terms of amount of reac- 59]. Based upon typical bond energies mentioned above
tion per unit of energy input, i.e. for either production of the approximate limit for single bond breaking is of order
reactive species or destruction of target compounds, reac- 10-6 mol/J and the reaction of ozone can approach this
tors that utilize gas phase discharge coupled to either thin
Locke 196

TABLE I
DATA ON ENERGY YIELD, BEST CASES SELECTED AND ADAPTED FROM THE REVIEW[8]

Discharge Electrode
Chemical P (W) EY (mol/J) EY (g/kWh) Reference Notes
type configuration
streamer-like needle[7]-plate
phenol 26.9 1.5E-08 4.9E+00 [60] O2 gas bubbles
in water in water
streamer
phenol over water 1.4E-08 4.7E+00 [61]
corona
hybrid gas in and over O2 gas phase, Fe2SO4
phenol 1.2E-08 4.0E+00 [37]
and liquid liquid liquid, activated carbon
oxacillin DBD falling film 2 1.9E-08 2.7E+01 [62]
pentoxifylline DBD falling film 1.2 2.0E-08 2.0E+01 [63] tap water
dichlorophenol Pulsed corona water spray 1.7E-08 1.0E+01 [64]

value (indirect plasma). From this data alone, direct ·OH, O3, H2O2, and even reductive chemical species[9,
plasma treatment, while it can be competitive, does not 22, 65-71]. In the case of H2O2, perhaps the easiest spe-
appear to offer significant advantages over indirect plas- cies to measure (at least downstream of the plasma or in
ma (used to form ozone) and other advanced oxidation the reactor liquid effluent), the energy yield data also
methods that directly form reactive radical species. Nev- gives the highest efficiencies for low power pulsed dis-
ertheless, this comparison is not complete because other charges with water spray[72]. H2O2 is of most interest
factors including more complete degradation, mineraliza- because it is a relatively stable carrier of ·OH; the direct
tion, and the cost of formation of reactive species need to reactivity of H2O2 with organic compounds is generally
be considered. More research is needed to consider all much less than that of ·OH. In reactors where plasma
of these factors and we urge researchers to go beyond volume is small, and where the plasma is very inhomo-
the tendency of reporting only initial compound degrada- geneous, the formation of H2O2 in the plasma and at the
tion and percent removal. We also suggest that re- plasma-liquid interface is important and H2O2 can be
searchers concentrate on the reactor configurations that considered to carry the ·OH from the plasma to the bulk
have the highest reported efficiencies (falling film and solution. This occurs typically in lower power plasma
water spray) and to perform experiments with a range of reactors with streamer or streamer-like plasma channels.
chemical species some of which are common to other However, in cases where the plasma may be more ther-
methods for ease in comparison. Comparisons including mal in nature, e.g. electrohydraulic discharge or arc and
amounts and types of reaction products formed and de- spark-like, the ·OH reactions with a target pollutant occur
grees of mineralization are clearly needed. inside the plasma region and the formation and role of
Plasma discharge applied directly to water containing H2O2 are relatively insignificant.
organic compounds was initially considered to have ad- The existence of ·OH in various plasma discharges
vantages over indirect plasma conditions because of 1) with water has been clearly demonstrated by optical
in-situ generation of reactive chemical species (·OH and emission spectroscopy and quantitative measurements of
other reactive species), 2) simultaneous formation of UV the rates of production and energy yields have utilized a
light, 3) possible formation of locally high temperature variety of chemical probes (see reviews[19, 22]). Quan-
and pressure regions that in some cases reach the critical tification by use of chemical probes requires careful
point, 4) in some gas-liquid configurations simultaneous choice of target compounds so as to not affect the solu-
formation of reactive species in the liquid and in the gas tion properties and to consider the effects of the probe
phase, 5) in some conditions of high power electrohy- concentration. Streamer-like discharge directly in water
draulic discharges lead to shockwaves, and 6) for biolog- and combined in and over water gave energy yields for
ical species the local electric fields can disrupt cellular ·OH of 10-10 to 10-9 mol/J[66, -67], while discharges in
membranes and lead to cell inactivation. While all of the the gas phase over water gave 3x10-8 mol/J[73] and
above factors have been experimentally demonstrated 6x10-9 mol/J[61]. In comparison, the primary yield of
and some aspects have been quantitatively measured, ·OH in electron beam irradiation[74] is 3x10-7 mol/J and
further work is still necessary to develop our understand- that for ultrasonic discharge[75] in water the yield is
ing of all the conditions which control the relative im- 5x10-10 mol/J. From this rather limited set of data, elec-
portance of each factor and to enhance performance effi- trical discharge directly in the liquid appears to fall be-
ciency. We deal with some of these issues below. tween electron beam irradiation and ultrasound. Much
more data on the rates and energy yields for ·OH and
other radicals is needed for electrical discharges with
IV. CHEMISTRY – ACTIVE CHEMICAL SPECIES FORMATION liquid water including the main recommended reactor
types mentioned above. The previous work has shown
For some types of reactors significant effort has al-
the effects of probe concentrations, solution conductivity,
ready been devoted to determining the formation rates
and the input power and applied voltage for selected re-
and energy yields for active chemical species, including
actor types, with discharges of 1 J/pulse directly in the
197 International Journal of Plasma Environmental Science & Technology, Vol.6, No.3, DECEMBER 2012

liquid and discharges over liquid surfaces, but data on bulk phase chemical reactions[86-95]. A number of gas
other types of reactors and for broader ranges of condi- phase models with the addition of water vapor have also
tions is lacking. It is strongly recommended that re- been developed. In the early ozone generation literature,
searchers report work using similar radical probes and the role of water on affecting the yield of O3 and on the
emissions spectroscopy and to compare their experi- generation of H2O2 was recognized for gas phase dis-
mental results with data already reported. charges in air[96, 97]. More recently, the effects of wa-
Radicals formed in electrical discharge reactors can ter vapor on the formation of H2O2 were extensively ana-
be detected using optical emissions spectroscopy. How- lyzed for gas phase discharge in helium[98]. Other mod-
ever, to quantify the radical formation other techniques els to consider the effects of water molecules on nitrogen
including the use of laser induced fluorescence (LIF) and oxide chemistry have also been reported (see for re-
the addition of various chemical probes can be utilized. views[19, 21, 22]). Although further work is still need-
LIF has been used for measuring ·OH in air plasma[76], ed, even in the case of gas phase plasma with water mol-
plasma containing water vapor[77-79], and in plasma ecules, the modeling approaches are relatively well estab-
over liquid surfaces[69, 80]. Electron spin resonance lished. The approach of Bruggeman and coworkers is
(ESR) with radical spin traps has been used to determine particularly useful and should be extended to other gas
·OH, and other radicals, in various advanced oxidation compositions such as pure argon or mixtures of argon
technologies including, for example, photochemical and and oxygen[98] .
photocatalytic reactors[81], ultrasonication[82] and ozo- Models of electrical discharges formed in the gas
nolysis[83]. Since LIF and ESR require relatively com- phase over the liquid surface are very much needed to
plex experimental setups and specialized operations, help in analyzing and interpreting the chemical mecha-
chemical probes inserted in the liquid and removed for nisms. Analyzing reactions that occur at the gas-liquid
analysis have also been utilized. Chemical probes such interface is an open area with only a few studies dealing
as hydroxyterephthalate can be measured using fluores- directly with this topic[99] (see also the reviews[19, 22]
cence spectroscopy and have been used to quantify plas- and the primary reference[100]). Modeling is necessary
ma discharges directly in liquid water and over water to assist in determining the location of the major reac-
surfaces[66, 67, 84]. Other chemical probes with known tions and in analyzing the transfer of various reactants
reactivity to ·OH such as dimethyl sulfoxide (DMSO), and products between the gas and liquid phases. Exper-
phenol, and methanol or other alcohols can also be used, imental work coupled with mathematical modeling is
but care should be taken in assessing reaction products. very much needed to determine interphase transport of
For example, methanol can lead to large amounts of H2 radicals and other reactants and products. The literature
gases which can affect certain gas phase discharges and on atmospheric chemistry and physics is a good place for
DMSO can produce ionic products which may affect the guidance with these issues[101-109] where particular
discharge in the liquid at high concentration and conduc- attention has been placed on the measurement of interfa-
tivity. Other probes including I- and Br- have been used cial transport and equilibrium of radicals at the air-water
in similar studies of sonolysis[85]. It is important to use interface[110-115].
a variety of radical probes, to vary the probe concentra- Models of gas phase discharges inside bubbles in liq-
tion, and to compare with the literature already reported uids have been developed using the approaches of gas
on radical formation. phase plasma[116-120]. Filamentous discharge propaga-
In addition to the comments above regarding meas- tion along the inside of the bubble surface in the liquid
urements of radicals, it is important to report sufficient and some aspects of the gas liquid-chemistry have been
data so that comparison with existing methods and as- simulated. However, detailed analysis to describe the
sessment of the scientific and engineering merit of the formation of active species, H2O2 and ·OH, in support of
work can be made. Table II summarizes some of the key experimental studies[112, 122] is needed.
recommendations for the methodologies for further ex- Models of electrical discharge directly in the liquid
perimental work in this field and Table III provides rec- phase have recently been extensively reviewed[54].
ommendations on some specific experiments that are Models of electrical discharges of high power (typically
needed. kW) and/or of spark and arc-like nature generally focus
on the electrohydrodynamic phenomena including for-
mation of shockwaves, variations of temperature and
V. MODELING pressure, and generation of UV light. Coupling of the
physical phenomena to the chemical reactions in such
In order to interpret experimental data, to assess reac-
systems has not been extensively developed and this area
tor performance, and to design reactors for scale-up and
needs substantial work. It is likely that the extensive
applications, it is important to develop accurate models
models developed for ultrasonic reactors which couple
of the electrical discharge[86]. Because of the widely
the physical hydrodynamics with the chemical reactions
varying time and length scales related to the physics of
can be used as models for further development of models
discharge propagation and the chemistry of plasma reac-
for these types of electrical discharges. In the case of
tions, plasma modeling is generally a very complex topic.
streamer-like discharges of relatively low power (<100
In gas phase plasma systems, modeling efforts are rela-
W), some coupling of the physical conditions of higher
tively highly developed to include the multi-scale phe-
nomena from the fundamental streamer physics to the
Locke 198

TABLE II
RECOMMENDATIONS FOR APPROACHES AND PROCEDURES TO USE IN EXPERIMENTAL STUDIES

RECOMMENDATION REF.
Data showing only decoloration of a dye or initial degradation of a chemical species is not of further interest unless substantial [8, 49]
improvements in reactor efficiency are reported or new insights into the mechanisms for the reactions are uncovered. There are
already enough papers showing that plasma contacting with liquid causes dye decoloration and organic compound degradation.
The same comment applies to experiments on the addition of iron salts that induce the Fenton reaction; it is no longer sufficient
to show that this causes organic compound degradation since this has been well established in the literature.

When new reactor types or operating conditions are given, it is imperative that the input power, the energy per pulse (if pulsed),
and the input voltage and current be given. All power supply specifications including frequency, capacitance, and the wave-
forms should be reported. All reactor operating conditions including gas and liquid flow rates and volumes must be given for
proper assessment.

When chemical degradation is reported, researchers should provide energy yield. In the case of comparing a single species from [8, 129]
one case to another case energy yield in g/kWh is sufficient. However, when comparing different types of chemical species
energy yield in mol/J or molecules/eV are preferable. In order to compare with conventional advanced oxidation methods elec-
trical energy per order (EEO) reduction should be provided.

Measurements of ozone and hydrogen peroxide should be conducted in cases where there is no organic compound addition.
Where possible, control experiments with the addition of either ozone or hydrogen peroxide alone should be reported for chemi-
cal degradation experiments. Formation of byproducts and/or the reduction in total organic carbon should be given for experi-
ments with organic target compounds.

Data on pH, conductivity, temperature, and any observed changes of these properties during the experiments should be given in
order to make proper comparison and to analyze the role of the chemistry. The gas composition should also be specified clearly.

Where possible, optical emission spectroscopy should be reported, and if possible the density and energy of the electrons deter- [131-141]
mined. Data is needed on ·OH and other radical generation rates. Spectra just showing the emissions lines are not sufficient
since many studies have already clearly established the existence of such species. Analysis of the chemical reactions and com-
parison with measurements of stable species should be further developed[130]. Determination of electron energy and density
using, for example, Stark broadening should be conducted.

Determination of electrode effects. Measurement of metals or other materials sputtered by electrodes into the liquid (or gas) by [142-147]
the discharge should be conducted. Such materials can cause catalytic effects as well as represent possible contamination of the
treated fluid. The potential lifetimes of electrode materials need to be assessed.

TABLE III
RECOMMENDATIONS FOR SPECIFIC EXPERIMENTS

RECOMMENDATION REF.
Chemical degradation and radical production studies should focus on water film and water spray reactors since they have the [9, 49]
largest potential for improved energy efficiency. The role of gas composition should be carefully considered and experiments
with pure argon and pure oxygen are recommended. When air is used, control experiments showing the effects of nitrogen ox-
ides should be conducted and measurements of nitrogen oxides should be made. In all cases with oxygen, control experiments
showing the roles of ozone should be conducted.

Data on the production rate of ·OH and other oxidative and reductive radicals over a wider range of input power as well as solu-
tion conditions is needed, particularly for film and water droplet reactors. The role of the gas composition (and liquid properties)
must be carefully considered. The formation of stable species such as O3 and H2O2 should be measured in the same conditions as
those for the radical measurements.

Further work is needed for a wider range of chemical species, but experiments with phenol as a comparison are particularly [148]
useful for new reactor configurations because there is a lot of existing data on phenol that can be used. Work with dyes is of
interest, but care should be taken to consider the effects of pH on dye absorbance and further understanding of the reaction
mechanisms (i.e., where on the dye molecule ozone or ·OH radical attack). Reaction product measurements by chromatographic
techniques are preferable to measuring only UV absorption spectra. Further data for compounds that have limited reactivity with
ozone, but high reactivity with ·OH is of interest. Compounds spanning a wide range of reactivity with ·OH are also of interest.

Chemical degradation and radical production studies should focus on water film and water spray reactors since they have the [9, 49]
largest potential for improved energy efficiency. The role of gas composition should be carefully considered and experiments
with pure argon and pure oxygen are recommended. When air is used, control experiments showing the effects of nitrogen ox-
ides should be conducted and measurements of nitrogen oxides should be made. In all cases with oxygen, control experiments
showing the roles of ozone should be conducted.

temperature to the chemical reactions have been reported, Further development of reactor models that include
but the physical models require more detail. both the chemistry and the physics of the discharges are
needed. It is unlikely that one model, or even modeling
199 International Journal of Plasma Environmental Science & Technology, Vol.6, No.3, DECEMBER 2012

TABLE IV
MODELING NEEDS FOR PLASMA INTERACTING WITH WATER (INCLUDING VAPOR AND CONDENSED PHASES)

RECOMMENDATION REF.
Gas phase discharge with water vapor molecules. Extension of the zero-dimensional global model of this reference to other gas [98]
compositions including, but not limited to, pure argon, pure oxygen, and various mixtures. The model can be extended to flow
reactors and one-dimensional cases.

Gas phase discharge with water droplets. Extension of the zero-dimensional global model of the reference above to include [149, 150]
chemical reactions in argon and/or oxygen and mass transfer between the gas and liquid for experiments as given in these refer-
ences. The model can be extended to flow reactors and one-dimensional cases.

Gas phase discharge inside bubbles immersed in water. Extension of basic plasma models developed in these references for air [116-120]
bubbles in water for different gas compositions including, but not limited to, pure argon, pure oxygen, and various mixtures.

Gas phase discharge over liquid water surface. Extension of the basic plasma model developed for plasma formed over a dielec- [99]
tric surface to account for liquid water chemical properties and water vapor reactions.

Accurate determination of plasma and gas and liquid temperatures and pressures should be made in order to accurately predict
chemical reaction rates. Plasma electron collisions with major chemical species should be included in the models.

Models of direct streamer-like discharges in liquid water need to be extended to include more detailed and accurate simulations [54]
of local temperatures and pressures and to include coupling between the plasma region and the bulk solution.

Models of arc and spark discharges in liquid water need to be extended to include more details on the chemical reactions occur- [54]
ring in the plasma channels and the interactions with the bulk liquid phase.

Models should be closely coupled to experimental results. Some aspects of the modeling may require model-data fitting, but
predictions should be made and results compared with experimental data not used in the fitting in order to establish model validi-
ty.

approach, can be used for all of the various types of the VII. CONCLUSION
electrical discharges that contact the liquid phase. Never-
While there is a growing interest in plasma contacting
theless, more work is needed to couple the physics and
with liquids[126, 127] it is also clear that further under-
the chemistry in order to give realistic descriptions of the
standing of the basic physics and chemistry, particularly
temperatures and pressures that affect the chemical reac-
at the gas-liquid interface is needed[128]. The major
tions. Table IV lists some specific recommendations for
engineering challenges include electrical power supply
further modeling and simulations studies needed for
design, conversion of input power to discharge power,
plasma with liquid water in environmental applications
and electrode materials and configuration. While the
and most of these comments are based upon the recent
basic processes for the formation of reactive species such
review[54].
as ·OH, H2O2, and O3 are understood, there remains a
need for more careful analysis of the most promising
reactor configurations for efficient pollution treatment.
VI. BIOLOGICAL INTERACTIONS
In the case of water treatment, thin water film and aero-
The interactions of plasma with biological cells and sol droplet reactors have the most promise and more ex-
tissue is dominated by the reactions of the gas phase perimental data over wider ranges of conditions is needed.
plasma with liquid water and there is much in common We urge researchers to conduct more thorough studies of
between chemical degradation and biological inactiva- the reaction chemistry by analyzing reaction products
tion[21, 39, 44, 123-125]. The formation of reactive ox- and to report all important details for their studies. There
ygen (ROS) and reactive nitrogen (RNS) species are very is also a need for further mathematical modeling of both
important. ROS and RNS can directly and indirectly the physical and chemical aspects of electrical discharges
affect plasma induced chemical reactions. Direct reac- interacting with liquid water. Modeling efforts for gas
tions involve attack of the plasma generated radical on phase plasma over liquid surfaces are needed. For dis-
the target chemical or biological entity. Indirect effects charges directly in the liquid phase, models of sparks and
include changes in solution pH and conductivity which in arc generally neglect the chemistry while models of
turn affect radical reactivity or post-plasma reactions streamer-like discharges include reactions, but need more
whereby degradation continues for long time periods, detail on the physics. This short review has attempted to
more than several hours, after the plasma has been turned outline various suggestions where further experimental
off. The analysis of the chemical species and reactions efforts should be directed and where modeling efforts are
initiated by electrical discharges in and in contact with needed.
liquid water should also enhance our understanding of
the interactions of plasma with biological materials.
Locke 200

ACKNOWLEDGMENT [20] Chang, J. S. 2008. Physics and chemistry of plasma pollution

control technology. Plasma Sources Science & Technology
We thank the National Science Foundation (CBET- 17:045004.
0932481) and Florida State University for support. [21] Lukes, P., J. L. Brisset, and B. R. Locke. 2012. Biological effects
of electrical discharge plasma in water and in gas-liquid envi-
ronments. In Plasma chemistry and catalysis in gases and liquids.
V.I. Parvulescu, M. Magureanu, P. Lukes, editors. Wiley-VCH
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