CHLORINE DIOXIDE,

OZONE, COLD PLAZMA,

DENSE PHASE CARBON
DIOXIDE: MECHANISM,
APPLICATIONS,
THEORY

1 Glin Kltr
Sinem Yava

FDE-511
December 20, 2010
 CHLORINE DIOXIDE

What is chlorine dioxide?

Production, storage?
Usage
Applications
Mechanism
Studies

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CHLORINE DIOXIDE??
Chemical-physical properties:
Consist of one chlorine atom
and two oxygen atoms
Boiling temperature: 11C
High redox potential
Very good solubility in water
(higher than chlorine and
ozone) : 0.8 g/100 mL (20 C)
No pH sensitivity
Yellowish gas or liquid

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CHLORINE DIOXIDE
PRODUCTION AND STORAGE
Chlorine dioxide generators

Never handled in concentrated form,

but almost always used as a dissolved
gas in water in a concentration range
of 0.5 to 10 grams per liter.
At concentrations > 15% volume in air
at STP, it decomposes into chlorine and
oxygen.
Solubility increases at lower
temperatures: use chilled water (5 C
or 41 F)

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CHLORINE DIOXIDE
USAGE
municipal drinking water
treatment,
removal of bio fouling, such as
Legionella, from cooling towers,
various disinfection applications,
animal drinking water
purification,
food processing,
Chlorine dioxide can be used for
process plant disinfection and the
removal of bacteria from water
used in food processing
prevention of membrane fouling,
destruction of bacteria in building
drinking water systems,
waste system odor control,
paper processing,
industrial cleaning, and 6
paper manufacturing
 CHLORINE DIOXIDE
APPLICATIONS
Anti-microbial
Chlorine dioxide, both in solution and in the
gas phase, kills a broad range of pathogens,
from viruses and bacteria to bacterial
spores and encysted parasites to yeasts and
fungi.

Mold remediation
Chlorine dioxide, both in solution and in the
gas phase, kills mold, including toxic molds
such as Stachybotrus and Aspergillus.

Biofilm control
Chlorine dioxide effectively penetrates
biofilm, and kills the resident bacteria.

Odor control
Chlorine dioxide effectively oxidizes many
odor-causing compounds, especially
mercaptans and sulfur compounds.
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CHLORINE DIOXIDE
APPLICATIONS
Metals oxidation
Chlorine dioxide oxidizes
undesirable metals found in
watere.g., manganese, ironand
converts them from a soluble state
to an insoluble state, which enables
their removal by precipitation or
filtering.

Color removal
Chlorine dioxide effectively removes
the color from many compounds,
such as may be found in drinking
water or wastewater.

Oxidation of THM/HAA precursor

Chlorine dioxide is used to pre-treat
raw water, in order to destroy
compounds that would react with
chlorine in downstream processes;
this reduces production of
trihalomethanes (THM), haloacetic
acids (HAA) and other chlorinated
organic compounds. 8
CHLORINE DIOXIDE
EFFECTIVE ON:

E. coli
Legionella HOSPITALS (!)
Pneumophilia
Streptococcus Facalis
Bacillus
Clostridium
Amoebae
Giardia
Cryptosporidium
Pseudomonas
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CHLORINE DIOXIDE
INACTIVATION OF BACTERIA AND VIRUSES
Two inactivation mechanism:
In the first disinfection mechanism, chlorine dioxide reacts readily with amino
acids cysteine, tryptophan, and tyrosine, but not with viral ribonucleic acid
(RNA) (Noss et al., 1983; Olivier et al., 1985). From this research, it was
concluded that chlorine dioxide inactivated viruses by altering the viral capsid
proteins. However, chlorine dioxide reacts with poliovirus RNA and impairs
RNA synthesis (Alvarez and OBrien, 1982). It has also been shown that
chlorine dioxide reacts with free fatty acids (Ghandbari et al., 1983). At this
time, it is unclear whether the primary mode of inactivation for chlorine
dioxide lies in the peripheral structures or nucleic acids. Perhaps reactions in
both regions contribute to pathogen inactivation.
The second type of disinfection mechanism focuses on the effect of chlorine
dioxide on physiological functions. It has been suggested that the primary
mechanism for inactivation was the disruption of protein synthesis (Bernarde
et al., 1967). However, later studies reported the inhibition of protein synthesis
may not be the primary inactivation mechanism (Roller et al., 1980). A more
recent study reported that chlorine dioxide disrupted the permeability of the
outer membrane (Aieta and Berg, 1986). The results of this study were
supported by the findings of Olivieri et al. (1985) and Ghandbari et al. (1983),
which found that the outer membrane proteins and lipids were sufficiently
altered by chlorine dioxide to increase permeability.
Gross physical damage to bacterial cells or viral capsids has not been observed
at the low concentrations of chlorine dioxide typically used to disinfect drinking 10
water.
CHLORINE DIOXIDE
PARAMETERS:

Factors influencing the antimicrobial

effectiveness of gaseous ClO2 are (Han et al.,
2001):

Its concentration
Contact time
Relative humidity
Temperature

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CHLORINE DIOXIDE
FOODS STUDIED:
For decontamination of fresh-
cut fruits and vegetables
(Zhang and Farber, 1996;
Singh et al., 2002; Wu and
Kim, 2007)
Meat (Pohlman et al., 2002)
Seafoods (Kim et al., 1999;
Andrews et al., 2002)

Gas better than liquid ClO2

Penetration better
Greater contact
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CHLORINE DIOXIDE
LIMITS (!)
WHO, Guidelines for Drinking-Water Quality, 3rd edition :
Acceptable recommended value for ClO2 has not been established
Chlorites/ Chlorates: 0.7 mg/l
WHO 2005 Chlorite and Chlorate in Drinking Water
WHO/SDE/WSH/05.08/86

EPA (United States Environmental Protection Agency):

Max. 0.8 mg/l ClO2, 1.0mg/l chlorite

HSC (Health and Safety Commision GB)

Max. 0.5 mg/l ClO2+chlorite+chlorate

Guideliness on drinking water-Germany

Max. Dose ClO2:0.4 mg/l, max. Residue ClO2:0.2 mg/l, max. Chlorite
residue:0.2 mg/l

WHY?
BECAUSE OF FORMATION OF INORGANIC COMPOUNDS LIKE
CHLORITES AND CHLORATES!
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CHLORINE DIOXIDE
DETECTION
Spectrophotometry Ion Chromatography (IC)

Amperometric Titration DPD (N,N-diethyl-p-phenylenediamine)

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 OZONE

What is ozone?
Production, storage?
Usage
Applications
Mechanism
Studies

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OZONE?
Triatomic molecule,
consisting of three oxygen
atoms
Boiling point: -111.9 C
Solubility in water: 0.105
g/100mL (0 C)
Bluish gas with pungent
odor
Strong oxidizing properties

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OZONE
PRODUCTION AND STORAGE
Ozone is produced commercially by passing electrical discharges or
ionizing radiation through air or oxygen.
The production rate changes according to the feed gas
If feed is air, 1-3% of effluent is ozone
If feed is pure oxygen, 6% ozone yield
The production rate can not be increased further; that the rates of
formation and production are equal (Manley and Niegowski, 1967)
Ozone spontaneously degrades back to oxygen atoms thus can not be
stored.

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OZONE
APPLICATIONS
Agriculture, fish, farming
Cooling towers and ozone
use
Chemical synthesis
Water treatment with ozone
Fire restoration with ozone
Soil remediation
Food processing
Carbon scrubber
pretreatment
Groundwater remediation
Enzyme plants
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OZONE
APPLICATIONS
Grain treatment
Food preservation
most powerful oxidizer available
instantly destroys microbes
eliminates chemical storage
environmentally friendly
stops mold spores
does not affect product taste
no harmful by-products
can be used in air and water
Bacteria/Pathogen reduction
Drinking water for agriculture
Wastewater treatment
Livestock manure
Livestock lagoons
Ozone and irrigation

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 OZONE
INACTIVATION OF BACTERIA AND VIRUSES
Cell envelopes:
Oxidizing polyunsaturated fatty acids, membrane-bound
enzymes, glycoproteins, glycolipids
Leakage of cell components, disruption of cell permeability,
and eventually cell lysis (Scott and Lesher, 1963; Murray et
al., 1965)
Bacterial spore coats:
Coat proteins are removed, thus inactivation occurs rapidly

Enzymes:
Due to oxidation of sulfhydryl groups in cysteine residues
(Chang, 1971)
Nucleic material:
Open the circular plasmid DNA, reduce its transforming
ability, produce single and double strand breaks in plasmid
DNA, lastly decrease transcription activity (Mura and
Chung, 1990)
Mutations? (S. cerevisiae, E.coli)

Viruses: Khadre MA, Yousef AE, Kim

JG, 2001, Microbiological
Attack capsid protein, liberate and inactivate nucleid acid Aspects of Ozone Applications 23
(Sproul and Kim, 1980; Kim et al., 1980) in Food: A Review, Journal of
Food Science, Vol 66, p. 1242-
T4 and f2 bacteriophages inactivated 1252
CHLORINE DIOXIDE
PARAMETERS:

Factors influencing the antimicrobial

effectiveness of ozone are (Khadre et al., 2001):

Temperature
pH value
pH range: 5.7-10, stable at low pH than high pH
Ozone consuming compounds
Concentration
Time

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Rather than being G(+) nor G(-), the effect of ozone
application is mostly varied within strains, showing that, it
is a treatment available only for a specific organism.

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OZONE
FOODS STUDIED:
Beef and beef brisket fat (Gormon et al.,
1997)
Poultry meat (Dave, 1999)
Salmon (Goche and Cox, 1999)
Apples (Achen and Yousef, 2001;
McLoughlin, 2000)
Strawberries (Lyons-Magnus 1999)
Lettuce (Kim et al., 1999)
Juices (Kim et al., 2001)

Microbial studies show generally 2-log

reduction and an important reduction in
spoilage

Prevention of surface contaminants

On meat
On produce
Packaging materials
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EFFECT OF CHLORINE DIOXIDE AND OZONE ON FOOD QUALITY

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COMPARISON OF CHLORINE
DIOXIDE AND OZONE
CHLORINE OZONE
DIOXIDE
Disinfection: bacteria Moderate Excellent
and viruses (water Moderate Excellent
treatment)
Environmentally No Yes
friendly
Color removal Good Excellent
Carcinogen Likely Unlikely
Formation
pH effect Variable Lowers
Organics oxidation Moderate High
Comlexity Low High
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Capital cost Low High
Micro flocculation None Moderate
 COLD PLASMA

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WHAT IS PLASMA?
Plasma is a state of matter
similar to gas in which a
certain portion of the
particles are ionized.
The basic premise is that
heating a gas dissociates its
molecular bonds, rendering
it into its constituent atoms.
Further heating leads to
ionization (a loss of
electrons), turning it into a
plasma: containing charged
particles, positive ions and
negative electrons.
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 DIFFERENCES BETWEEN GAS AND PLASMA
Property
Electrical conductivity
Independently acting species
Velocity distribution
Interactions
Gas
Very low
Air is an excellent insulator until it
breaks down into plasma at electric
field strengths above 30 kilovolts per
centimeter.
One
All gas particles behave in a
similar way, influenced by
gravity and by collisions with
one another.
Maxwelian
Collisions usually lead to a
Maxwellian velocity distribution
of all gas particles, with very
few relatively fast particles.
Binary
Two-particle collisions are the
rule, three-body collisions
extremely rare.
Plasma
Usually very high
For many purposes, the
conductivity of a plasma may be
treated as infinite.
Two or three
Electrons, ions, protons and
neutrons can be distinguished by
the sign and value of their
charge so that they behave
independently in many
circumstances, with different
bulk velocities and
temperatures, allowing
phenomena such as new types of
waves and instabilities.
Often non-Maxwellian
Collisional interactions are often
weak in hot plasmas and
external forcing can drive the
plasma far from local
equilibrium and lead to a
significant population of
unusually fast particles.
Collective
Waves, or organized motion of plasma,
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are very important because the particles
can interact at long ranges through the
electric and magnetic forces.
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PARAMETERS
Size (m)
Lifetime (s)

Density (particles /m3)

Temperature (K)

Magnetic fields (Tesla)

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WHAT IS COLD PLASMA?
Cold plasma is a partly ionized gas, which is
generated in a high-voltage electric field in a
low pressure. The surface structure and
properties of polymers, fibres and fabrics can be
modified by low-temperature plasma techniques.
Wet chemical treatments can be replaced by
plasma processes, which need only small
amounts of selected chemicals.

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WHAT IS COLD PLASMA?
Cold plasma is obtained at low pressure
(vacuum). This condition allows reactions to take
place in a temperature range of 20 to 30 C
inclusive while in conditions of atmospheric
pressure these are possible only at temperatures
of hundreds of degrees.

In fact, despite the low temperature of the gas,

the temperature of the electrons is very high
(from 20 to 50.000 K) due to the length of the free
run of the particles.
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HOW IS IT PRODUCED?
Two electrodes, each made of a thin copper ring attached to
the surface of a glass disk(the disk is about 2.5 centimetres
across and has a small hole at its centre).
These electrodes are then inserted into a dielectric tube
and are separated by a gap that can be varied between 0.5
and 1 centimeter.
When helium gas is injected into the tube and short (less
than one microsecond) high-voltage pulses are applied to
the electrodes, a discharge is ignited in the gap between the
electrodes. This produces a plasma plume that is ejected
through the hole in the outer electrode.
The plume can be up to 5 centimetres long, with the length
depending on the flow rate of the helium and the size of the
voltage pulses.
The plume remains at room temperature and can be 37
touched by bare hands.
Schematic of the plasma jet developed by Forster et al.
38
Schematic of the plasma jet developed by Laroussi and
Lu. The electrodes are circular copper rings attached to centrally
perforated alumina disks. The plume, which can reach
lengths in excess of 50 mm, is launched from the central orifice 39
(3 mm in diameter). The voltage pulses are 500 ns wide with
repetition rates of few kHz.
PROPERTIES OF A GOOD COLD PLASMA
Ability to work at room
temperature and
atmospheric pressure

Hand held

Non-heating up while
operating

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APPLICATIONS OF COLD PLASMA
Decontamination in biomedical and food areas
Surface treatment

Effect on fresh fruits (active packaging of apples)

Modification of textile products

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SURFACE TREATMENT
At low and atmospheric pressure,
Wettability modification : hydrophobic or hydrophilic
character,
Biocompatibility improvement,
Antifog treatment, Anti-UV treatment,
Persistent and resistant treatments

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STERILIZATION

Scanning electron micrographs of

A - untreated control,
B - 5 min argon plasma treated,
C - 1 min argon +14.2% O2 plasma
treated Escherichia coli cells seeded
in filter papers.

Sterilization effects of
atmospheric cold plasma brush
Q. S. Yua and C. Huang

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STERILIZATION
Survival curves of (A)
Escherichia coli and
(B) Micrococcus luteus on filter
papers after plasma exposure
with different amount of oxygen
addition.

Sterilization effects of
atmospheric cold plasma
brush
Q. S. Yua and C. Huang

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STERILIZATION

Arc-Free Atmospheric Pressure

Cold Plasma Jets: A Review
Mounir Laroussi,* Tamer Akan

Escherichia coli 45
ACTIVE PACKAGING OF APPLE

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ACTIVE PACKAGING OF APPLE
Plasma-processed vanillin on
apple substrate. There are
approximately 80 nodules/ mm2.

Cold Atmospheric-Pressure
Plasmas Applied to Active
Packaging of Apples

Sulmer A. Fernndez
Gutierrez, Patrick D. Pedrow, 47
Marvin J. Pitts, and Joseph
Powers
ADVANTAGES OF COLD PLASMA
Get very specific surface properties
Chemical modification of surface solely, without
changing the bulk properties
With low quantities of gas and without using
dangerous, toxic, or polluting chemical products, we
develop a specific surface chemistry driven by the
choice of treatment gases
Treat various substrate shapes, with adapted reactor
Treat films with high running speed and continuous
flow, by atmospheric pressure electrical discharges.
Since the atmospheric plasmas are operated in open
air, the use of these plasmas can easily overcome the
limitations imposed by the currently available
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vacuum-based plasma sterilizers.
 DENSE PHASE CO2

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WHAT IS DENSE PHASE CO2
CO2 exists in its supercritical state above 31 C
and 7.34 MPa.
Below this critical temperaturepressure
combination, CO2 exists in the subcritical liquid
or gaseous state depending on the specific
temperaturepressure combination.
Supercritical CO2 has properties of both liquid
and gaseous CO2 with altered viscosity,
diffusivity and solubility, resulting in improved
dissolving power.

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APPLICATIONS
Decaffeination in coffees
Environmentally friendly
solvent for dry cleaning as
compared to more traditional
solvents such as hydrocarbons
and perchloroethylene.
Extraction solvent in the
creation of highly-potent hash
oil, known as honey oil.
In laboratories, supercritical
carbon dioxide is used as an
extraction solvent
Supercritical fluid extraction has
also been used in determination
of hydrocarbon components in
water.
Inactivation of microorganisms 52
MECHANISM OF INACTIVATION
Theories explaining the inactivating mechanism
of CO2 involve

a cytoplasmic pH decrease,
explosive cell rupture,
modification of a cells membrane,
inactivation of key enzymes
extraction of intracellular substances.

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PARAMETERS OF INACTIVATION
Exposure time,
Pressure,

Temperature,

Initial number of cells,

Initial pH of medium,

Water activity,

Cell growth phase or age,

Species of microorganisms,

Type of treatment system

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ADVANTAGES OF DENSE PHASE CO2
Carbon dioxide is often an ideal choice because of

mild critical properties (Tc = 31 C, Pc = 74 bar),

non-toxic,
non-flammable,
inexpensive
unregulated

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REFERENCES

Benarde MA, Snow WB, Olivieri VP, and Davidson B, 1967, Kinetics and Mechanism of Bacterial
Disinfection by Chlorine Dioxide, Vol. 15, Applied Microbiology, p. 257-265
Benarde MA, Israel BM, Olivieri VP, and Granstrom ML, 1965, Efficiency of Chlorine Dioxide as a
Bactericide, Applied Microbiology, Vol. 13, p. 776-780
Taylor RH, Falkinham III JO, Norton CD, and LeChevallier M, 2000, Chlorine, Cloramine,
Chlorine Dioxide, and Ozone Susceptibility of Mycobacterium avium, Applied and Environmental
Microbiology, Vol. 66, p 1702-1705
Vandekinderen I, Devlieghere F, Camp JV, Kerkaert B, Cucu T, Ragaert P, Bruyne J, Meulenaer
B, 2009, Effects of food composition on the inactivation of foodborne microorganisms by chlorine
dioxide, International Journal of Food Microbiology, Vol 131, p 138-144
Mahmoud BSM, Linton RH, 2008, Inactivation kinetics of inoculated Escherichia coli O157:H7
and Salmonella enterica on lettuce by chlorine dioxide gas Food Microbiology, Vol. 25, p. 244-252
Gomez-Lopez VM, Rajkovic A, Ragaert P, Smigic N, Devlieghere F, 2009, Chlorine dioxide for
minimally processed produce preservation: review , Vol 20, p. 17-26
Khadre MA, Yousef AE, Kim JG, 2001, Microbiological Aspects of Ozone Applications in Food: A
Review, Journal of Food Science, Vol 66, p. 1242-1252
Sproul OJ, Kim CK. 1980, 1980, The mechanism of ozone inactivation of waterborne viruses.
Report (W81-00315, OWRT-B-013-ME/2), Order No. PB81-127334). From Government Rep
Announce-Index (U.S.)1981. 81(5),861.
Chang SL. 1971. Modern concept of disinfection. J Sanitation Eng Div 97:689-707
Scott DBM, Lesher EC. 1963, Effect of ozone on survival and permeability of Escherichia coli. J
58
Bacteriol 85:367-376
Murray RG, Pumela S, Elson HE. 1965. The location of the mucopeptide of sections of the cell wall
of Escherichia coli and other gram negative bacteria. Can J Microbiol 11(3):547-560.
REFERENCES CONTD
Laroussi M, Akan T, 2007,Arc-Free Atmospheric Pressure Cold Plasma Jets: A
Review Plasma Process. Polym., 4, 777781
Yua Q. S, Huang C, Hsieh F., Huff H. Duan Y. Sterilization effects of
atmospheric cold plasma brush, 2006 Applied Physics Letters, 88
Fernndez-Gutierrez S. A., Pedrow PD, Pitts MJ, Powers J,2010, Cold
Atmospheric-Pressure Plasmas Applied to Active Packaging of Apples, IEEE
Transactions on Plasma Science, vol. 38, NO. 4, 958-960
Sturrock, Peter A 1994, Plasma Physics: An Introduction to the Theory of
Astrophysical, Geophysical & Laboratory Plasmas, Cambridge University
Press.
National Research Council (U.S.). Plasma 2010 Committee, 2007, Plasma
science: advancing knowledge in the national interest , National Academies
Press. pp. 190193.
Liao H, Hu X, Liao X, Chen F, Wu J, 2007, Inactivation of Escherichia coli
inoculated into cloudy apple juice exposed to dense phase carbon dioxide,
International Journal of Food Microbiology 118 126131
GunesG, Blum LK , Hotchkiss JH, 2005,Inactivation of yeasts in grape juice
using a continuous dense phase carbon dioxide processing system, J Sci Food
Agric 85, 23622368

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THANK YOU SO MUCH....

DO YOU HAVE QUESTIONS?

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