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Peroxyacetic Acid : A Potent Food Industry Sanitizer

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 Indian Food Industry Mag
Vol 32 No 3, May-June 2013
Peroxyacetic Acid : A Potent Food Industry Sanitizer
Gawande H M1*, Dhotre AV2, Shendurse A M3 and Khodwe N M4
1&3
College of Dairy Technology Warud (Pusad), Dist- Yavatmal, (M.S.), India. 445 204.
2&4
Department of Dairy Engineering, College of Dairy Technology, Warud (Pusad).
*E-mail: gawande.hm@gmail.com
Abstract
Cleaning and sanitation is an inevitable food
processing operations. Though it does not directly
contribute to profit, it is matter of industrial attention
because of the stringent legal food standards. Various
technologies and ingredients are emerging as useful in the
cleaning and sanitation in food industry. Different cleaning
and sanitation agents are also being tried to improve
efficiency at lower cost. PAA is such a chemical that has
been tried as sanitizer in food industry. It is emerging as
better alternative to the chlorine sanitizers. Properties like
low corrosiveness, greater microbial lethality and
biodegradability adds towards its choice as sanitizer. If
proper safety measures are taken, PAA can prove to be a
better option as sanitizer.
Key Words: PAA, sanitizer, cleaning, peracetic acid,
oxidizing.
Introduction
During past decade, production of food has
become complex because of the voluminous production,
automation and requirement of prolonged shelf life. The
focus on healthy food has resulted in more pressure on
manufacturers to limit the use of chemical preservatives.
The stringent food quality standards demand efficient
operation along with sanitary practices in processing
plants. The word sanitary is derived from the Latin word
‘sanitas’ meaning health. So, sanitary refers to anything
that contains health or preservation of health and non
sanitary means injuries to health or that is unhealthful.
Sanitization is the process of reducing microbiological
contamination to levels confirming to public health
requirements. It conveys the idea of disinfection without
any residual harm to subsequent users and elimination of
aesthetically objectionable contamination. In the food
industry, cleaning and sanitization of all food contact
surfaces is an essential routine operation. Commonly, it
is done by using thermal treatment, radiation or chemical
sanitizers. Chlorine based sanitizers are widely used in
food industry.
TARs
Peroxyacetic Acid (PAA) is also known for its germicidal
properties for a long time but it has found food industry
application in recent years only. It is being promoted as
a potent chlorine replacement as food industry is as a
sanitizer. PAA is used to control deposit, odor and bio-
26
films on food contact surfaces and as a microbial control
agent for both food contact surfaces and direct contact
with fruits and vegetables. In comparison to other most-
used sanitizers in the food industry, PAA may be more
compatible with organic handling than the use of halogen-
based sanitizers and disinfectants such as chlorine bleach,
iodine-phosphorous (iodophors) or quaternary ammonium
compounds (QACs). Chlorination can seriously damage
aquatic life and form chlorinated hydrocarbons having
carcinogenic and mutagenic properties (Arturo-Schaan et
al., 1996). PAA degrades rapidly, leaves little residue and
decomposes into relatively harmless naturally-occurring
substances (Evans, 2000).
Properties of PAA
Peroxyacetic acid (C2H4O3) is popular by various
names as Peracetic Acid, Acetyl Hydroperoxide, Acetic
Peroxide, Desoxon, Ethaneperoxic Acid, Peroxyethanoic
Acid, Persan and Bioside but basically, it is an aqueous
mixture of acetic acid and hydrogen peroxide. Although
PAA is true active ingredient, the hydrogen peroxide
fraction aids in stabilizing the PAA and contributes
additional oxidation capacity to overall formulation. It is
very strong oxidizing agent with higher oxidation potential
than chlorine or chlorine dioxide. It can react violently
with acetic acid anhydride, olefins (e.g., mineral oil) and
organic matter (NTP, 2000). Liquid PAA is clear and
colorless with no foaming capability and has strong
pungent acetic acid odor. It has acidic pH (2.8) and
weighs 0.924 Kg/cm3. It is stable upon transport, exhibits
low surface tension. It is effective and stable between pH
1 to 9 with slightly increased rate of hydrolysis above pH
8.3. Initial degradation products are acetate and water
whereas finally biodegraded to carbon dioxide, oxygen and
water. PAA breaks down to acetic acid, water and oxygen
that naturally occur in the agroecosystem (Alexander,
1991). It has the advantage over chlorination, which can
seriously damage aquatic life through the formation of
mutagenic or carcinogenic chlorinated hydrocarbons
(Arturo-Schaan, 1996). It is more persistent than chlorine-
based disinfectants, but less than quaternary ammonium
compounds (Evans, 2000). It can have a longer residual
activity than chlorine (Gruetzmacher and Bradley, 1999).
It doesn’t contribute to taste and odor of the product due
to very low concentration used for sterilization. Efficacy
of PAA is unaffected at temperature as low as 2.2 ºC for

most species. It completely disintegrates into water and
oxygen at temperature above 73.89 ºC. There are no
known hazardous or toxic byproducts associated with its
use. It is probably more effective as a disinfectant in
aqueous solutions (Greenspan and Margulies, 1950) than
on biofilms (Ntsama et al., 1997) or in organic waste
slurries (Bohm et al., 1983). It may be a better biocide
for viruses (Quiberoni et al., 1999) and bacteria (Meyer
and Meltz, 1999) than it is for fungi (Colgan and Johnson,
1998). Some bacteria, such as spore formers, are more
resistant (Lensing and Oei, 1985).
PAA usually occurs with hydrogen peroxide and acetic
acid in an aqueous solution. Stock commercial
preparation usually contain a synthetic stabilizer such as
1-hydroxyethyliden-1,1diphosphoric acid (HDPE) or 2, 6
pyridinedicarboxylic (dipicolonic) acid to slow the rate
of oxidation or decomposition (Kurschner and Diken,
1997).
Limitations of PAA
• Not compatible with chlorine
• PAA is consumed by sulfites and sulfides.
• Reduced half life above pH 8.5
• Rapid decomposition in the presence of metal.
• Cannot be stored in mild steel or contaminated
containers.
Methods of Preparation
Peracetic acid (PAA) is produced by reacting acetic
acid and hydrogen peroxide. The reaction is allowed to
continue for up to ten days in order to achieve high yields
of product according to the following equation.
Due to reaction limitations, PAA generation can
be up to 15% with residual levels of hydrogen peroxide
(up to 25%) and acetic acid (up to 35%) with water up
to 25%. Additional methods of preparation involve the
oxidation of acetaldehyde or alternatively as an end
product of the reaction of acetic anhydride, hydrogen
peroxide and sulfuric acid.
Additional methods of preparation involve the
oxidation of acetaldehyde (Budavari, 1996) and reaction
of tetraacetylethylenediamine (TAED) in the presence of
an alkaline hydrogen peroxide solution (Davies and Deary,
1991). These sources appear to be used more frequently
27
Indian Food Industry Mag
Vol 32 No 3, May-June 2013
in pulp, paper and textile manufacture (Pan, Spencer and
Leary, 1999).
Mode of Action
The primary mode of action is oxidation, PAA
disinfects by oxidizing of the outer cell membrane of
vegetative bacterial cells, endospores, yeast and mold
spores. The mechanism of oxidation is the transfer of
electrons, therefore the stronger the oxidizer, the faster
electrons are transferred to the microorganism and the faster
the microorganism is inactivated or killed. PAA works by
penetrating the cell wall and cell membrane and oxidizing
the H-S and S-S bonds in the cell’s enzyme. Microbes are
then unable to function and die. Because the cells are
destroyed from the inside-out via oxidation, they can’t
develop immunity or mutant to counteract it. The PAA is
superior to even hydrogen peroxide in its antimicrobial
activity (Evans, 2000).
PAA inactivates enzymes that are responsible for
discoloration and degradation, such as peroxidase in the
browning of potatoes (Greenspan and Margulies, 1950).
Among the model organisms that show significant
reductions in populations after exposure to PAA are
Bacillus cereus (Blackiston et al., 1999); B. subtilis
(Leaper, 1984; Blackiston et al., 1999; Lindsay and von
Holy, 1999); B. stearothermophilus (Blackiston et al.,
1999); Clostridium botulinum (Blackiston et al., 1999);
C. butyricum (Blackiston et al., 1999); C. sporogenes
(Blackiston et al., 1999); Ditylenchus dipsaci (Hanks and
Linfield, 1999); Enterococcus faecium (Andrade et al.,
1998); Escherichia coli (Arturo-Schaan et al., 1996),
including E. coli O157:H7 (Farrell et al., 1998), Fusarium
oxysporum (Hanks and Linfield, 1999); Gluconobacter
oxydans (Winniczuk and Parish, 1997), Lactobacillus
plantarum (Winniczuk and Parish, 1997), L. thermophilus
(Langeveld and Montfort-Quasig, 1996); Leuconostoc
mesenteroides (Winniczuk and Parish, 1997); Listeria
monocytogenes (Mosteller and Bishop, 1993; Restaino et
al., 1994); Pseudomonas aeruginosa (Restaino et al., 1994;
Lambert et al., 1999); P. fluorescens (Mosteller and
Bishop, 1993; Lindsay and von Holy, 1999);
Saccharomyces cerevisiae (Winniczuk and Parish, 1997);
Salmonella typhimurium (Restaino et al., 1994);
Staphylococcus aureus (Restaino et al., 1994; Lambert et
al., 1999); Streptococcus delbreuckii subsp bulgaricus
(Langeveld and Montfort-Quasig, 1996); and Yersinia
enterocolitica (Mosteller and Bishop, 1993)
Uses
PAA was patented in 1950 to treat fruits and
vegetables to reduce spoilage from bacteria and fungi
destined for processing (Greenspan and Margulies, 1950).
TARs
It has since been used in systems to disinfect recirculated
wash water used to handle fresh produce (Lokkesmoe and
Olson, 1995). It is used to treat bulbs (Hanks and Linfield,
1999), to disinfect potting soil, clean irrigation equipment,
 Indian Food Industry Mag
Vol 32 No 3, May-June 2013
(Larose, 1998) and in seed treatment to inactivate fungal
or other types of plant disease. While, there is a long
history of experimental field use as a fungicide /
bactericide, efficacy has only recently been established
(Hei, 2000). Peracetic acid is effective at reducing
Escherichia coli O157:H7 on apples when used in a wash
and as a chemical sanitizer (Wright et al., 2000).
Peracetic Acid appears to be an effective
microbiocide for disinfecting equipment, seeds, plant
materials and as a post-harvest treatment of fruits and
vegetables. PAA is stabilized equilibrium solution that is
approved for numerous uses, including circulation,
cleaning and industrial sanitization of equipments such
as tanks, pipelines, evaporators, fillers, pasteurizers,
aseptic machines, etc as follow;
• All types of Process Equipment in dairy including
farm equipment.
• Wineries, vineyards, breweries and beverage
plants.
• Meat, poultry, seafood and vegetable processing
and packaging plants.
• Use as a fogging adjunct for critical disinfection
in packaging rooms.
• Cleaning, sanitizing and continuous disinfection
of UF and RO membranes.
• Industrial circulating cooling water for both open,
closed and semi closed loops
• Waste water treatment (as an outstanding sulfide
oxidizer and inhibitor, odor control agent,
disinfectant and cleaner.)
• Other non-porous food or non-food contact
surfaces such as conveyors and doorway foamer
systems.
• Pulp and paper process water slime and deposit
control and specialty bleaching.
• Drip irrigation tape line cleaner and algaecide.
• Broad spectrum efficacy against gram-negative and
gram-positive bacteria, E. coli O157:H7, Listeria,
Salmonella, Pseudomonas and many other
organisms.
There are no known hazardous or toxic by-
products associated with its use and provides operational
ease. No rinse is required at levels up to 100 ppm for
many fruits and vegetables and up to 500 ppm for
equipment sanitation uses.
Cooling Water: PAA solutions find particular
advantageous use in cooling water systems because it is
a very powerful oxidizer (second only to ozone). PAA is
TARs
lipid soluble making it an effective on-line and off-line
cleaner. Higher doses can be used to remove slime mass
accumulation. It does not create halogenated by-products
or THM’s, does not react with ammonia and much other
nitrogen-based chemistry and does not contribute to the
28
conductivity or TDS of the blow-down or bleed off stream.
PAA consumes alkalinity, allowing higher cycles of
concentration compared to hypochlorite. For most surface
discharges, quenching is not required. PAA is compatible
with organic scale and corrosion inhibitors. The threshold
level for most algae and slime forming organisms is 1-2
ppm active PAA. Effective pH ranges are as high as 9.5,
but the optimum is below 8.3.
Sanitation: When used as the primary sanitizer in
processing facilities, the PAA formula does not contribute
to wastewater TDS or total salt levels and does not
interfere with most wastewater chemical treatment
programs or systems. There are no known microbial
mutation or resistance responses to PAA. It can be used
at concentrations up to 200 ppm active PAA without
requiring a “water rinse”. Normal use rates are 80 ppm
with contact times of 1 minute to achieve a 99.999%
microbial kill.
Agriculture: PAA solutions are finding specialty use as
a fungicide for daffodil and flower bulbs, a biodispersant
and slime inhibitor for flume systems and as a drip
irrigation line cleaner and algaecide. When used as a drip
line cleaner, the PAA breaks down in soil within minutes,
releases (adds) active oxygen and does not contribute a
salt or conductivity (EC) loading in the root zone. At levels
above 10 ppm, the product will dissolve calcium and add
mild acidity to the soil. When compared to chlorine, PAA
will not depress crop yields.
Wastewater: PAA has been used successfully as an
additive for sludge debulking, algae control, chemical
enhancement for sulfide removal and prevention, as a
supplement to UV disinfection and odor eliminator. PAA
use costs are lower than chlorine for treating raw and
physico-chemically treated effluents. For biologically
treated effluents, use cost is higher (but with similar
efficacy results), yet PAA does not create THM precursors
or most of the DBP’s (disinfection by-products) associated
with the use of chlorine.
Detection
Testing is accomplished using the DPD Total

Chlorine method. The results are multiplied by 1.07 for
PAA equivalence. Detection limit with this method is 0.5
ppm.
The hydrogen peroxide content is determined by
an oxidation reduction titration with ceric sulfate,
according to equation 1. After the endpoint of this titration
has been reached, an excess of potassium iodide is added
to the solution. The hydroiodic acid formed in acidic
media reacts with peracetic acid to liberate iodine,
according to equations 2. A standard solution of sodium
thiosulfate is used to titrate the liberated iodine, as shown
in equation 3. The endpoint of this titration is used to
calculate the peracetic acid content.
Safty and Regulatory Aspects:
PAA is an irritant of the skin, eyes, mucous
membranes and respiratory tract (NTP, 2000; Budavari,
1996; Lenga, 1985). It is toxic by inhalation, ingestion
or if absorbed through skin and corrosive at concentrations
above 10 % and irritant at concentrations below 2 %.
When heated to decomposition it emits acrid smoke and
toxic fumes of carbon monoxide and carbon dioxide. The
vapor is heavier than air and can travel a considerable
distance to a source of ignition and flash back (NTP,
2000). It is considerably unstable and may explode on
heating. It is incompatible with strong oxidizing agents,
acetic anhydride, alkenes and organics. Therefore, safety
glasses, adequate ventilation, gloves, face protection and,
if using significant quantities, full body protection against
a possible explosion is needed.
FDA approved it for direct food contact, for use
in wash water or to assist in the peeling of fruits &
vegetables (21CFR173.315) and also as sanitizer on food
contact surfaces (21 CFR 178.1010). Peracetic acid is not
explicitly listed as GRAS by FDA but it arguably benefits
human health by controlling food-borne pathogens
(Cherry, 1999). The maximum residues for wash water
used for fruits and vegetables are 80 ppm (21 CFR
173.315) and that allowed on a food contact surface are
200 ppm (21 CFR 178.1010). The efficient (minimal) use
of PAA as disinfectant in a HACCP program requires
constant monitoring but is feasible (Schultz, 1992).
Conclusion
PAA has found food industry application in recent
years and is being promoted as a potent chlorine
replacement. PAA is relatively stable at use strengths of
100 to 200 ppm. Other desirable properties include:
absence of foam and phosphates, low corrosiveness,
tolerance to hard water and favorable biodegradability.
PAA solutions have been shown to be useful in removing
biofilms. While precise mechanisms of mode of action
have not been determined, it is generally theorized that
the PAA reaction with microorganisms is similar to that
of Hydrogen Peroxide. PAA, however, is highly active
against both gram-positive and gram-negative
29
Indian Food Industry Mag
Vol 32 No 3, May-June 2013
microorganisms. As germicidal activity of PAA is highly
affected by pH, rise in pH especially above 7-8 should
be prevented. PAA has a pungent odor and the
concentrated product (40 %) is a highly toxic, potent
irritant and powerful oxidizer. Thus, care must be taken
in its use. PAA has broad-spectrum impacts on
microorganisms, is an irritant and may cause other health
problems if handled improperly. However, if proper safety
precautions are taken, PAA can be the principle alternative
chemical sanitizers and disinfectants.
Further Reading
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Andrade, N.J., Bridgeman, T.A. and Zottola, E.A. (1998)
Bacteriocidal activity of sanitizers against
Enterococcus faecium attached to stainless steel as
determined by plate count and impedance
methods. Journal of Food Protection, 61: 833-838.
Arturo-Schaan, M., Sauveger, F., Mamez, C., Gougeon,
A. and Cormier, M. (1996) Use of peracetic acid
as a disinfectant in a water-treatment plant: Effect
on the plasmid contents of Escherichia coli strains.
Current Microbiology, 32: 43-47.
Blackistone, B., Chuyate, R., Kautter Jr, D.,
Charbonneau, J. and Suit, K. (1999) Efficacy of
oxonia active against selected spore formers.
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Bohm, R., Britzius, E. and Strauch, D. eds. (1983)
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