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Low Oxygen and Inert Gas Processing of Foods

a a
K. Sanjeev & M. N. Ramesh
a
Food Engineering Department , Central Food Technological Research Institute , Mysore,
India
Published online: 26 Apr 2007.

To cite this article: K. Sanjeev & M. N. Ramesh (2006) Low Oxygen and Inert Gas Processing of Foods, Critical Reviews in Food
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 Critical Reviews in Food Science and Nutrition, 46:423–451 (2006)
Copyright
C Taylor and Francis Group, LLC
ISSN: 1040-8398
DOI: 10.1080/10408390500215670
Low Oxygen and Inert Gas
Processing of Foods
K. SANJEEV and M. N. RAMESH
Food Engineering Department, Central Food Technological Research Institute, Mysore, India
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INTRODUCTION
Since the discovery of the basic vitamins and their many
forms efforts have been made to retain them in foods during
their post harvest handling, commercial processing, distribu-
tion, storage, and preparation (Gregory, 1996). During the last
few years, the nutritional importance of antioxidants such as
carotenoids, tocopherols, and vitamin C in foods has found in-
creased interest due to their possible role in the prevention of
human diseases as cancer, atherosclerosis, immune depression,
and cataract (Micozzi et al., 1990, 1992; Byres and Perry, 1992;
Canfield et al., 1993; White et al., 1993; Mutto et al., 1995; van
Poppel et al., 1995). The status of vitamins during processing
is receiving more attention. A comprehensive overview of the
influence of processing on the vitamin status is given by Karmas
et al., 1988.
Vegetables are an important and low-cost food containing
low levels of fat and high levels of vitamins, minerals and fibres
(Masrizal, 1997), and a variety of substances and several specific
compounds with protective properties for human health (Scott
et al., 1996). Dried, canned, and frozen foods/vegetables are a
very important part of our food supply. However, the processing
of products rich in antioxidants for final consumption leads to a
loss of relevant compounds as carotenoids and vitamin, lowering
the nutritional quality of the produce.
Foods are usually processed under normal atmosphere. The
composition of dry air is indicated in Table 1.
The main vitamin losses occur due to (Rumm-Kreuter et al.,
1990):
• Water solubility and mass transfer (leaching)
• Heat sensitivity
• Enzymatic oxidation
Address correspondence to Dr. M. N. Ramesh, Scientist, Food Engineering
Department, Central Food Technological Research Institute, Mysore 570 013,
India. E-mail: mnr64@rediffmail.com
423
For preservation of any vegetable produce, it must be properly
processed immediately after harvesting. Although vegetables
processing has a very long tradition, several products usually
suffer distinct losses in quality during processing. Foods rich
in carotenoid suffer significant color changes during processing
due to the presence of oxygen in the processing atmosphere,
which reduce their market value considerably.
After microbial spoilage, oxidation leading to overt rancidity
is the second most important cause of food spoilage. The pro-
tection of foods from oxygen is the basic principle upon which
antioxidant protective technologies are based. Many of these
are drawn from experiences with lipid oxidation. The high wa-
ter solubility of vitamin C (Mueller, 1990) and its heat sensitivity
compared to most other nutrients may cause problems during the
preservation of vegetables (Belitz and Grosch 1988; Kozar et al.,
1988). Oxidation of food ingredients as vitamins, pigments, and
aroma compounds is one of the most important causes of quality
loss during food processing and is the main deteriorative reac-
tion in microbiologically safe foods as dry and frozen products
(Anderson and Lingnert 1997). Membrane lipids, vitamins, and
pigments are oxidized by enzymes or by auto-oxidation.
Physical Phenomena of Oxidative Destruction of Nutrients
There has been some interest in the study of storage life of
and the period processed products that retain maximal or near-
maximal nutrient value. Nutrient value has usually been infor-
mally defined as preservation of important nutrients in the food
product, including vitamins, enzymes, proteins and complex car-
bohydrates. The main cause of degradation in raw/fresh foods
is oxidative degradation due to free radicals known as reactive
oxygen species (ROS), which include peroxide ions, superoxide
anions, and other aggressive oxygen species, including O3 and
other short-lived oxygen radicals. It is well known that the degree
of exposure during processing to heat and ambient air contain-
ing oxygen, particularly tiny bubbles of oxygen which are finely
 424 K. SANJEEV AND M. N. RAMESH
Table 1 Composition of dry air
Gases Symbol % by volume
Nitrogen N2 78.08
Oxygen O 20.95
Argon Ar 0.93
Carbon dioxide CO2 0.033
Neon Ne 0.0018
Helium He 0.00052
Methane CH4 0.0002
Krypton Kr 0.00011
Nitrous oxide N2 O 0.00005
Hydrogen H2 0.00005
Source: http://scifun.chem.wisc.edu/chemweek/airgases/airgases.html.
dispersed as in repeated grinding, blending, or mastication, can
rapidly accelerate the formation of these ROS components, and
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thus aging of the food product and its nutrient quality.
The primary measure of oxidative degradation of the fresh
food products is oxidation-reduction potential (also called
“redox”) or ORP. ORP measures the degree of oxidation or re-
duction (reduction is absence of oxidation and is tantamount
to anti-oxidant power) of a water-based substance, and the ORP
scale ranges from -1,200 (strongly reducing) to +1200 (strongly
oxidizing.) Most raw organic green vegetable juices prepared
from a good juicer will show an initial ORP from −100 through
+160, indicating a fairly good store of primitive (reducing) an-
tioxidants in the juice (the pH will usually be about 5.6 to 5.9,
indicating presence of plant acids). Raw organic carrot juice will
sometimes show an ORP as low as −170 to −200 (and a pH of
about 6.8 or higher, since carrots are not as acid as other vegeta-
bles), as will some raw organic wheat grass juice. However, most
green juices and vegetable juice mixes show an ORP between
−100 and +160. As a juice ages and gradually oxidizes (e.g.,
due to any of these factors: heat, exposure to air and light, time),
the ORP will increase steadily, finally reaching a “settling” zone
of +350 to +450. As a juice oxidizes, it steadily loses nutrient
value. In general, the ORP of raw organic green juices in storage
should remain at or below an ORP of +180, although an ORP
of up to 210 might be acceptable.
Since air is about 21% oxygen, it will be a potent and ma-
jor force in accelerating oxidation of the stored product packed
in containers. If the containers are packed with little or no air
space above the product (e.g., a full bottle, well-sealed), the ox-
idation can be avoided. The best way is to pack units that can
be consumed at once, instead of in bulk. Otherwise, as the prod-
uct is consumed and the level reduces, the headspace (dead air
space) above the product should be flushed and filled with an
inert gas prior to sealing the containers. This reduces the amount
of oxygen in the headspace to less than 1% (Pinto, 2000)
The Importance of Oxygen in Oxidative Destruction
of Ascorbic Acid
The kinetics of the oxidation reaction has been shown to be
first order with respect to ascorbic acid. Khan and Martell (1967)
have reported that the rate for spontaneous oxidation of ascorbic
acid in aqueous model system is proportional to concentration
of molecular oxygen down to 0.2 atmospheres of oxygen. The
monoionic species of ascorbic acid is found to be the only reac-
tive moiety toward oxygen at pH <7. The mechanism proposed
the direct participation of molecular oxygen in the spontaneous
oxidation of the ascorbate anion. In the same study, Khan and
Martell (1967) reported that the rate of ferric and cupric ion cat-
alyzed ascorbic acid oxidation were first order with respect to the
molecular oxygen concentration. Ford (1967) and Burton et al.
(1970) have reported that the level of residual oxygen present in
solution determines the stability of vitaminC in milk. Singh et al.
(1976) reported the rate of ascorbic acid destruction with oxy-
gen uptake to follow second order rate kinetics in the presence
of limited dissolved oxygen (1.0–8.71 ppm) in liquid infant for-
mula exposed to five light intensities (0–4284lux). The second
order rate constant increased as the initial dissolved oxygen con-
centration increased from 4.86 to 8.71 ppm. The rate of ascorbic
acid destruction as a function of initial dissolved oxygen con-
centration was constant in the absence of light. These results
were supported by the companion study of Mack et al.(1976)
which reported the kinetics of oxygen uptake to be first order in
presence of light. In the absence of light, the rate of ascorbic acid
loss was independent of initial dissolved oxygen concentration.
Processing under low oxygen atmosphere may lower the ox-
idative effects and maintain the nutritional value of the processed
foods. One of the possibilities in this context is to use airless dry-
ing. The alternatives for air less drying are
1. Superheated steam
2. Vacuum
3. Inert gas/atmosphere
Superheated Steam
Superheated steam system provides the advantages of high-
energy efficiency due to regeneration of heat and high heat trans-
fer leading to lower drying time besides, low oxygen conditions.
But, the important limitation is its high product temperature of
above 100˚ C, which is not suitable for heat sensitive foods.
Lower temperatures will lead to the condensation of steam on
to the product, which may increase the moisture content of the
product instead of decreasing.
Vacuum
The percentage of oxygen remaining with various degrees
of vacuum is indicated in Fig. 1. Atmospheric air is about one-
fifth oxygen, the remainder consisting mainly of nitrogen. As
absolute vacuum is approached, the residual oxygen reaches
a very low value. Commercial vacuum systems used on pro-
duction lines do not reach absolute vacuum, so there is always
some residual oxygen present. A vacuum of 91.175 kPa (27” of
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS
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Figure 1 Vacuum and residual oxygen. Source: Eselgroth (1951)
mercury) results in 2.09 % residual oxygen, and 97.929 kPa (29”
of mercury) vacuum leaves 0.69 % residual oxygen. Therefore,
in order to obtain a residual oxygen content of less than 1 per-
cent, a vacuum of better than 95 kPa (28” of mercury) is required
(Eselgroth, 1951). Creation of this vacuum requires huge
amounts of energy. Also, even if there is a microhole it will
lead to disruption of the vacuum as the atmospheric air may
enter the system.
Hence, the only suitable, practical alternative is to use inert
gas recirculation to maintain inert atmosphere.
Inert Gas
Inert gas has been used in food processing in a variety of ways.
The objective of the present review is to compile the different
applications of inert gas in food processing and the possibility
of low oxygen atmosphere processing.
LOW OXYGEN PROCESSING
Low Oxygen Drying
Success with the belt-trough dryer stimulated the idea of a
dryer design using recycled vapors of dehydration in a partially
closed system. Also, because oxidation is one of the causes of
nutrient losses during food processing a drying atmosphere con-
taining minimal oxygen could be an aid in the retention of greater
nutritive values for dried foods. Attempts were made to develop
low oxygen vapor drier to improve the retention of nutritive val-
ues of dried foods (Morgan et al., 1979). A schematic of the
dryer is indicated in Fig. 2. But the results were not consistent.
So, this requires more research.
425
Control of Enzymatic Browning in the Food Industry
Browning of raw fruits, vegetables, and beverages is a major
problem in the food industry and is believed to be one of the
main causes of quality loss during post harvest handling and
processing (Mathew et al., 1971). The mechanism of browning
in foods is well characterized and can be enzymatic or nonenzy-
matic (Walker, 1977). The formation of pigments via enzymatic
browning is initiated by the enzyme polyphenol oxides (PPO;
monophenol, L-DOPA: oxygen oxidoreductase; EC 1.14.18.10),
also known as tyrosinase, phenol oxidase, monophenol oxidase,
or cresolase. Endogenous PPO activity is present in foods that
are particularly sensitive to oxidative browning, e.g., potatoes,
apples, mushrooms, bananas, peaches, fruit juices, and wines.
Browning is more severe when the food has been subjected to
surface damage, which can result from cutting, peeling, com-
minuting, pureeing, pitting, pulping, or freezing. In uncut or un-
damaged fruits and vegetables, the natural phenolic substrates
are separated from the PPO enzyme by compartmentalization,
and browning does not occur.
The most effective method for controlling enzymatic brown-
ing in canned or frozen fruits and vegetables is to inactivate
the PPO by heat treatment, such as by steam blanching, but
this is not a particular alternative for treatment of fresh foods.
As browning is an oxidative reaction it can be retarded by the
elimination of oxygen from the cut surface of the fruit or veg-
etable. Although browning will occur rapidly when oxygen is
reintroduced. Exclusion of oxygen is possible by immersion in
deoxygenated water, syrup, brine, or by vacuum deoxygenation
(Guadagni, 1949), or coating of the food with surfactant (Obrero
et al., 1987). As oxygen is required by PPO at the site of wound-
ing to initiate the browning reaction, the use of O2 –impermeable
packaging or edible films may be useful in preventing the on-
set of browning. The exclusion of O2 is also used in juices and
wines by bottling them under nitrogen (Martinez et al., 1995).
INERT GAS PROCESSING
Inert Gases
The inert or noble gases are Helium, Neon, Argon, Krypton,
Xenon, and Radon. They make up a complete group (0) in the
Periodic Table and the properties of each member of the group
are closely related to the others. The noble gases make up 1%
of the volume of Earth’s atmosphere.
They are called inert gases because they do not usually react
with any other element. Most elements react with one another
because the combined atoms are more stable than the individual
atoms. In fact, the most stable state generally occurs when the
number of electrons in the outermost shell of an atom is eight.
Reactions occur so that atoms can achieve eight electrons, either
by losing electrons or gaining them from their partner. The noble
gases are so stable, and react so little because, unusually for
elements, the number of electrons in the outer part of the atom
completely fills the shell.
 426 K. SANJEEV AND M. N. RAMESH
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Figure 2 Schematic of low oxygen recycled vapor dryer. Source: Morgan et al. (1979)
In all but helium the number of electrons in the outer shell
is eight; for helium it is two, the maximum possible in its only
shell. Not all of the noble gases are equally stable. For example,
xenon can be made to combine with a few other elements, but
helium combines with none. The inert gases Helium and Neon
are lighter than air. Nitrogen has nearly the same weight as air.
The others are heavier. The term “inert atmosphere” usually
refers to a gaseous mixture that contains little or no oxygen and
primarily consists of non-reactive gases or gases that have a
high threshold before they react. Nitrogen, Argon, Helium, and
Carbon dioxide and common components of inert gas mixtures
can also be used for special purposes (www.meridianeng.com).
Inert Gas Drying
Most of the available publications on inert gas processing of
foods are in the form of patents without many details. {German
patent, DE 43 37 823 A1 (1995), British patent, 1 196 016
(1970), French patent FR 2 672 116 A1 (1992)}. Ramesh et al.
(1999) have evaluated the dehydration process using an inert
atmosphere of N2 and compared it with conventional hot air
drying. For cutting under inert gas to prevent oxidation dur-
ing slicing, the produce was cut in a special glove box un-
der a N2 atmosphere. Steam blanching efficiently provides an
oxygen free atmosphere. The blanched samples were immedi-
ately cooled in ice water to prevent further thermal stress. Af-
ter blanching, the vegetables were dried in a laboratory scale
convective drier either conventionally using hot air, or using
N2 gas.
Ramesh et al. (1999) have shown that though the differences
of heat and mass transfer coefficients of both drying processes—
conventional and inert gas—are marginal, the general trend in-
dicates higher transfer coefficients under inert gas, leading to
faster drying than conventional drying. The critical moisture
content was specific to a particular vegetable but always higher
for blanched products when compared with unblanched prod-
ucts.
It was observed that carotenoids increase by 12% in the case
of carrots and 22% in the case of paprika, during blanching
(Ramesh et al., 1999). The apparent increase of carotenoids
from fresh to blanched paprika and carrots has already been
observed and discussed by several authors. This increase can
be explained by the leaching of soluble solids during blanch-
ing. The discarded soluble solids represent approximately 30%
of the solid matter of fresh produce. This decreases the relative
amount of dry matter, thereby increasing the relative concentra-
tion of carotenoids (Weckel et al., Baloch et al., 1977, 1987).
Blanching causes about 2.7% loss in soluble solids; this leads
to an increase of 9.1% in carotenoid calculation (Baloch et al.,
1977). It is reported that this pseudo-increase in carotenoids may
vary from 20% to 50%, in some cases even up to 85%. The in-
crease may also be attributed to the more effective extraction
from the thermally treated tissues (Lee et al., 1982; Ueno et al.,
1982).
To circumvent this discrepancy, the true retention of nutrients
were calculated which provides the data on the proportion of nu-
trients remaining in the weight of the food before processing.
The methodology as suggested by Murphy et al. (1975) was ap-
plied and the true retention (TR%) of vitamin C and carotenoids
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS
were calculated. Vitamin C and total carotenoids were better re-
tained when the vegetables had been processed under inert gas.
This may be attributed to the protective atmosphere preventing
oxidation. Total carotenoid losses were reduced by 15% (abso-
lute) during inert gas processing of carrots and vitamin C losses
during inert gas processing of blanched paprika were reduced by
13% (absolute). In the case of potatoes, the reduction of loss of
vitamin C was marginal, about 2% (absolute). The differences
were significant at p of 0.05 obtained from Student’s t-test, ex-
cept for the carotenoid retention in blanched paprika (Ramesh
et al., 1999).
By inert gas processing, in particular inert gas drying, the
retention of vitamin C and carotenoids can be increased. As
vitamin C is frequently used as an indicator of the quality of
processed products (Tijskens et al., 1979) a better retention of
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vitamin C is indicative of an improved quality of a dehydrated
product. However, the economic feasibility of the process has to
be evaluated, after scaling up of the process at the commercial
level.
Drying in the inert atmosphere has a higher drying rate, dif-
fusion coefficient, mass, and heat transfer. The effect of inert
atmosphere was significant only in the case of vitamin C con-
tent. In other quality parameters the difference was very less.
However, the trend indicated better quality parameters of the
inert gas processing of the product (Ramesh et al., 2001). This
phenomenon needs to be further investigated.
INERT GAS PACKAGING AND STORAGE
Several methods can be used by the food processor to slow
down or inhibit deteriorative changes in foods, including chilled
storage, freezing, heat processing, drying, and the use of chemi-
cal additives and preservatives. However, the increasing energy
costs associated with freezing and drying, and growing con-
sumer concerns about preservatives have forced the food indus-
try to seek alternative methods of food preservation.
Modified Atmosphere Packaging (MAP)
MAP is the replacement of air (Composition indicated in Ta-
ble 1) in a pack with a single gas or mixture of gases; the propor-
tion of each component is fixed when the mixture is introduced.
No further control is exerted over the initial composition, and
the gas composition is likely to change with time owing to the
diffusion of gases into and out of the product, the permeation
of gases into and out of the pack, and the effects of product and
microbial metabolism.
Gases Used in MAP
The gases normally used in MAP are those found in the at-
mosphere: O2 , CO2 , and N2 . The choice of gas mixture used is
influenced by:
427
The microbiological flora capable of growing on the product
The product’s sensitivity to O2 and CO2
Color stabilizing requirements (e.g. the preservation of oxymyo-
globin in fresh meat and of nitrosomyoglobin in cured meat
products).
As an example, the changes in meat, fish, and poultry products
due to modified atmosphere storage are indicated in Table 2.
Oxygen (O2 ). O2 generally stimulates the growth of aero-
bic bacteria and inhibits the growth of strictly anaerobic bac-
teria, although there is a very wide variation in the sensitivity
of anaerobes to O2 . For certain products, the presence of O2
may even cause oxidative rancidity or color problems (e.g. fatty
fish and cured meats, respectively). For this reason, bacon is
typically modified-atmosphere packaged in 35% CO2 /65% N2 .
Low levels of O2 (∼0.5%) may cause browning of chilled meat
and cured meat products or cause greening in under-cooked
meat products (Church, 1993). Some researchers recommend
the inclusion of 5–10% O2 to certain MAP products (Hotchkiss,
1989), as an added safety factor against the growth of anaerobic
pathogens, in particular Clostridium botulinum. However, un-
less the atmosphere within the package is controlled, the gas
composition surrounding the product will change with time.
Furthermore, although Clostridium botulinum would not be ex-
pected to grow on the surfaces of products exposed to air, it
could grow a few millimeters below the surface, where anaer-
obic conditions may exist, and microenvironments may exist
where O2 levels are low enough to permit the growth of anaer-
obic microorganisms, even though the overall O2 level in the
package headspace might suggest otherwise. O2 supports the
growth of aerobic microorganisms; thus, removal of O2 from
the modified atmosphere will extend the microbiological shelf
life. O2 concentrations cause meat to have a temporary bright red
color.
Nitrogen (N2 ). N2 is used to displace O2 in packs and
storage vessels so as to delay oxidative rancidity and inhibit the
growth of aerobic microorganisms. Owing to its low solubility,
it is used as a filler gas to prevent pack collapse (snuffing). N2
atmospheres have been successfully employed (Bayes. 1950;
Kramer et al., 1966) for retarding oxidative deterioration of
perishable food products. N2 affects neither the microbiology
nor the color of the meat, but prevents packages from collapsing,
because the product does not absorb it. Sparging and blanketing
Table 2 Changes in meat, fish and poultry produced by modified atmosphere
storage
Enzymatic ageing processes: Unaffected.
Microbial spoilage: Increased carbon dioxide reduces the growth of aerobic
spoilage psychrotrophs by penetrating membranes and lowering intra-
cellular pH.
Fat oxidation: Reduced oxygen levels reduce the oxidation of fats, although
oxidation can still occur at low oxygen tensions.
Oxidation of myoglobin: Increased carbon dioxide promotes metmyoglobin for-
mation and color darkening.
Source: Smith et al., 1990.
 428 K. SANJEEV AND M. N. RAMESH

soybean oil and milk storage tanks with N2 also improves
product shelf life (Subramaniam, 1993).
Carbon Dioxide (CO2 ). CO2 is both water- and lipid-soluble
and is mainly responsible for the bacteriostatic effect on mi-
croorganisms in modified atmospheres. Although the bacterio-
static effect of CO2 has been known for many years, the precise
mechanism of its action is still a subject of considerable scientific
interest. The overall effect on microorganisms is an extension of
the lag phase of growth and a decrease in the growth rate during
the logarithmic growth phase.
This bacteriostatic effect is influenced by (Reddy and
Amstrong, 1992)
Concentration of CO2
Age
Load of the initial bacterial population
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the application of CO in the modified atmosphere packaging of
meat is indicated in Table 3.
Carbon Monodioxide (CO). The main function of low levels
of CO in modified atmosphere is to give meat a stable, cherry red
color, as a result of strong binding of CO to myoglobin and the
formation of carboxymyoglobin (Lentz, 1979). Although a sub-
stantial increase in the shelf life of meat can be obtained by using
various modified atmosphere, it is often limited by discoloration
due to the oxidation of myoglobin to metmyoglobin. This dis-
coloration can be prevented by the inclusion of a low level of CO
in the gas mixture. Carboxymyoglobin is more resistant to oxi-
dation than oxymyoglobin, owing to the stronger binding of CO
to the iron-porphyrin site on the myoglobin molecule (Wolfe,
1980). CO at concentrations of 1-5% increases the reduction of
metmyoglobin, even in the presence of air (Lanier et al., 1978).

Storage temperature A mixture of 2% CO and 98% air was very effective in stabiliz-
Type of product being packaged. ing the color of beef for 15 days, compared with 5 days in air
alone (El-Badawi et al., 1964).
Mechanism of CO2 Action
Toxicological Aspects of CO
The increased inhibitory effectiveness of CO2 at lower tem-
peratures is related to the dissolution of CO2 in the water phase Vacuum packaging is commonly used for the bulk storage,
of the meat. Since the solubility of gases is much higher at low transportation, and export of meat. However, vacuum packaging
temperatures, the CO2 concentration in the medium increases as has not proved to be a successful method for the retail packag-
the temperature decreases. The change in pH is due to the ad- ing of meat, because of the purple deoxymyoglobin color of the
sorption of CO2 on the food surface and subsequent ionization meat and the visible exudates that occurs in the packages (Bruce,
of the carbonic acid. The mechanism for the inhibition or de- 1990; Gill, 1996). Meat that is packaged in a vacuum cannot be
lay in growth of microorganisms in CO2 enriched atmospheres presented in the bright red oxymyoglobin state, which depends
has been postulated as interference by the carbonic acid and on the presence of a high concentration of O2 (Gill, 1996; Taylor
pH with enzyme systems attached to the cell; cellular dehydro- et al., 1990), or in the cherry red carboxymyoglobin state, which
genating enzymes; and/or mass-action equilibria for enzymatic requires CO to be included in the MA. One of the objections that
decarboxylation. (Brody, 1989) has been raised against the use of CO as a packaging gas is the
The major chemical problem when holding meats in CO2 potential hazard it might represent to workers in meat plants. Al-
enriched atmospheres has been surface discoloration. To over- though the use of pure CO for mixing in the plant would certainly
come this problem, high oxygen concentration in combination pose such a risk, the delivery of 1% CO in a mixture with 99% N2 ,
with CO2 has been suggested as a potential atmosphere. How- which has been the practice of gas suppliers to the Norwegian
ever, if higher than normal levels of oxygen are used, oxidative
rancidity becomes a problem. With high-moisture foods such as
Table 3 Applications of carbon monoxide (CO) in modified-atmosphere
meat, poultry meat, and seafood, excessive absorption of CO2 packaging of meat
can cause pack collapse. Pack collapse is used to good advan-
tage by the dairy industry in packaging wedges of hard cheese. Gas combinations (%)
The absorption of CO2 , by the cheese collapses the film around CO CO2 N2 O2 Air References
the cheese, which produces a pack with a soft vacuum appear-
2 98 EL-Badawi et al., 1964
ance. However, packaging in high CO2 concentrations can cause 1 50 49 Gee et al., 1978
increased drip in fresh meat, fluid release in ham, product sep- 0.5–10 90.0–99.5 Clark et al., 1976
aration in cream, physiological damage to fruit and vegetables, 1 51 18 30 Seidemann et al., 1979
and a “sherbet-like” taint in fatty fish (Parry, 1993). In the past, 1 50 25 24 Luno et al., 1996
adverse color reactions (e.g. graying/browning) were also at- 1 20 9 70 Luno et al., 1996
2 20 78 Renrre et al., 1993
tributed to packing in 100% CO2 , but it is now recognized that 1–5 95–99 Wolfe, 1980
these reactions are due to the low levels of oxygen in, the pack, 100 a Lentz, 1979; Clark et al., 1976;
rather than to the presence of CO2 per se (Church, 1993). CO2 Brewer et al., 1994
inhibits the growth of many microorganisms, but it has no ef- 0.4 60 40 Sorheim et al., 1997
fect per se on the color of meat (Renrre et al., 1993), CO2 is 0.3–0.4 60–70 30–40 Norwegian meat plants
absorbed in meat and fat tissue at a ratio of 1 liter of gas per a Exposure before packaging.
kg of tissue (Gill, 1988). A summary of the studies involving Source: Sorheim et al., 1997.
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS 429

meat industry, is recognized by the health authorities to be a
very safe handling procedure. Despite the long-term knowledge
of the many advantages of the use of CO as a component of mod-
ified atmosphere for meat, CO mixtures have not been adopted to
any great extent by the global meat industry. In many countries,
including the USA and countries within the EU, CO is presently
not permitted for use in the MAP of meat (Cornforth, 1994).
However, Norwegian food control authorities have not opposed
the use of CO as a packaging gas at concentrations of up to 0.5%.
Although CO preserves the color of the plant materials sub-
stantially by inactivating the polyphenoloxidase, it has little ef-
fect on the bacteria. Exposure of the apple plugs to the ethylene
oxide mixture proved satisfactory as far as the destruction of mi-
croorganisms is concerned but it did not inactivate the browning
enzyme system. Since plant products are generally high in mois-
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applications. Other gases that have been considered include SO2 ,
nitrous oxide (N2 O), nitric oxide (NO), ozone (O3 ), He, H2 , Ne,
Ar, propylene oxide, ethylene, and Cl2 , however, the use of these
gases has been limited by safety concerns, legislation, adverse
consumer response, cost and negative effects on the organoleptic
properties of packaged products (Church, 1993).
Gas Mixtures. Three types of gas mixtures are used in mod-
ified atmosphere packaging (Goodburn et al., 1988):
• Inert blanketing (N2 )
• Semi-reactive blanketing (CO2/ N2 or O2 /CO2 / N2 )
• Fully-reactive blanketing (CO2 or CO2 /O2 )
The combination of gases used depends on many factors such
as the type of product, packaging materials and storage tem-

ture, the difficulties encountered in the sterilization of dried ma-

perature. With regard to the product, the fat and moistures con-
terials or materials of low water content with this gas, as reported
tents, microbiological characteristics, respiration rate (horticul-
by Kaye (1949), were not evident in some study.
tural products), and color stabilizing requirements (red meat)
Argon. Packaging food with argon (Ar) instead of nitrogen
are critical factors. A summary of the gas mixtures for various
(N2 ) gas extends its shelf life, maintains its freshness and im-
products is shown in Table 4.
proves its overall quality, according to research presented at the
222nd national meeting of the American Chemical Society, the
world’s largest scientific society. Taste tests and other studies Controlled Atmosphere Packaging (CAP) and Storage (CAS)
have shown about a 25 % improvement in shelf life and quality of
argon-packaged foods such as potato chips, processed meats and The proportion of each gas is maintained (controlled) at the
lettuce, reports Dr. Spencer, of the British grocery chain Safeway original level introduced throughout the distribution cycle, re-
Stores. Some products, such as fresh pizza, have been improved gardless of temperature, or other environmental variations. CAP
by 40 to 50%. Ar is a safe, benign gas that has been used to pre- and CAS techniques are used primarily for the bulk storage and
serve wine. When foods such as potato chips are packaged, the transport of product, and require constant monitoring and con-
bag’s empty space is usually filled with N2 . Trace amounts of O2 trol of the gas composition within the package. With the devel-
remain, however, which causes food to oxidize—the chemical opments in high-barrier films, intelligent packaging, tray-ready
reaction responsible for potato chips becoming stale and cut ap- master packs, gas scavengers, and gas producers, the distinction
ples turning brown—and spoil. Spencer and his team found that between MAP and CAP has considerably tapered.
replacing N2 with argon removed Oxygen more efficiently, be-
cause Argon is denser than N2 and fills spaces more completely. Equilibrium Modified Atmosphere (EMA) Packaging
Despite argon’s superior results, it has taken nearly ten years to
make argon packaging commercially viable because, volume- This technique is used primarily for the packaging of fresh
for-volume, Argon is more expensive than N2 . When Ar is put fruit and vegetables. Either the pack is flushed with the required
through nitrogen systems, it does not work very well, so it is Table 4 Examples of gas mixtures for selected food product
needed to adjust the system to deliver the Ar as if it were a liq-
uid. In these modified packaging systems, argon is 4 times more Gas concentration (%)
Temperature
efficient at displacing air than nitrogen, making the difference in Product (◦ C) Oxygen Carbon dioxide Nitrogen
cost negligible. Argon also improves food safety. Not only does
Fresh meat 0–2 70 20 10
argon displaces oxygen, which many harmful pathogens need to
Cured Meat 1–3 0 50 50
grow, it also inhibits microbial oxidases-enzymes that increase Poultry 0–2 60–80 20–40 0
the rate of oxidation. CO2 is often added during packaging to Fish: Fatty 0–2 0 60 40
kill microbes, but it also spoils the flavor and freshness of foods. White 0–2 30 40 30
Ar enhances the effectiveness of CO2 by weakening microbes, Fresh Poultry 0–2 0 50 50
Fresh sausage 0–2 40 60 0
thereby enabling food suppliers to use less CO2 (Anon., 2001).
Cheese 1–3 0 60 40
Other Gases. A number of other gases such as ozone, car- Apples 4–6 2 1 97
bon dioxide, nitrogen trichloride, formaldehyde and nitrous Tomatoes 5–10 4 4 92
oxide have attracted attention as potential preservatives and Baked products 25 0 60 40
disinfectants with varying degrees of success (Dunn, 1957; Pizza 25 0 60 40
Dry Snacks 25 0 20–30 70–80
Phillips et al., 1958). A wide variety of other gases have been
investigated experimentally for their potential use in MAP Source: Smith et al. (1990).
 430 K. SANJEEV AND M. N. RAMESH
gas mix or the produce is sealed within the pack with no modifi-
cation to the atmosphere. Subsequent respiration of the produce
and the gas permeability of the packaging allow an equilibrium-
modified atmosphere to be reached.
Modified Atmosphere Generation
Passive Atmosphere Modification
Vegetables and fruits continue to respire after harvest, con-
suming oxygen and producing carbon dioxide and water vapor.
If the respiration characteristics of the commodity can be accu-
rately matched to the permeability of the film used for packaging
then a favorable modified atmosphere can be created passively
within the package, when an equilibrium concentration of oxy-
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gen and carbon dioxide is established. Equilibrium modified
atmospheres (EMA) containing 2–5% O2 and 3–8% CO2 has
been shown to:
Delay maturation and softening of vegetables,
Reduce chlorophyll degradation,
Microbial spoilage and
Enzymatic browning.
Active Packaging
The incorporation of certain additives into packaging film
or within packaging containers to modify the headspace atmo-
sphere and to extend product shelf life is referred to as active
packaging. These additives can be classified as:
Oxygen absorbents,
Carbon dioxide absorbents/emitters,
Ethanol emitters and
Ethylene absorbents.
This technology has considerable potential but is currently ex-
pensive. In the case of oxygen absorbents the cost of the additive
and the cost of automated insertion equipment needs to be con-
sidered. The subject has been extensively reviewed by Labuza
(1990) and Day (1991).
The “Sachet Generation”
Although vacuum/gas packaging can be used to extend the
shelf life and keeping quality of food, aerobic spoilage can still
occur in such packaged products. Depending on the level resid-
ual oxygen in the package headspace. The level or residual
oxygen in both gas- and vacuum-packaged products could be
due to factors such as the oxygen permeability of the pack-
aging material, the ability of the food to trap air, leakage of
air through poor sealing, and inadequate evacuation and/or gas
flushing. Several studies have shown that aerobic Pseudomonas
spp. and Aspergillus and Penicillium spp. can grow in an at-
mosphere of 1–2% oxygen, even in the presence of elevated
levels of carbon dioxide (Dallyn and Everton, 1969; Tabak and
Cookie, 1978; Smith et al., 1986). Such studies show that aerobic
microorganisms can tolerate very low concentrations of resid-
ual oxygen in the package headspace, and that additional control
measures are necessary to completely inhibit the growth of aero-
bic spoilage microorganisms in vacuum/gas-packaged products.
One such additional control method is through the use of oxygen
absorbents.
Oxygen Absorbents
Several types of oxygen absorbents are commercially avail-
able. One type, “Ageless,” made by the Mitsibushi Gas Chemical
Co., Japan, comprises of a range of gas-scavenger products de-
signed to reduce headspace oxygen levels to less than 100 ppm.
The basic system consists of finely divided iron powder con-
tained in a sachet (like a desiccant). The sachet material is highly
permeable to oxygen and water vapor and, under appropriate hu-
midity conditions, uses residual oxygen to form nontoxic iron
oxide. The oxidation mechanism can be expressed as follows:
Fe → Fe2+ + 2e−
1
/2 O2 + H2 O + 2e− → 2OH−
Fe2+ + 2OH− → Fe (OH)2
Fe (OH)2 + 1/2 O2 + 1/2 O2 H2 O → Fe (OH)3
Four main types (Z, S, FX, and E) of “Ageless” are available
for use with a wide range of foods. Type Z is designed for foods
with water activities of less than 0.85 and takes 1 to 4 days to
lower the residual oxygen to 100 ppm.
Commercial Application of CA & MA Storage
Several refinements in CA & MA storage have been made in
recent years to improve quality maintenance; these include creat-
ing nitrogen by separation from compressed air using molecular
sieve beds or membrane systems, low O2 (1.0 to 1.5%) storage,
low ethylene (<1 µL L−1 ) CA storage; rapid CA (rapid estab-
lishment of optimal levels of O2 and CO2 , and programmed
(or sequential) CA storage, e.g., storage in 1% O2 for 2 to 6
weeks followed by storage in 2 to 3% O2 for the remainder of
the storage period. Other developments, which may expand use
of atmospheric modification during transport and distribution,
include improved technologies of establishing, monitoring, and
maintaining CA, using edible coatings or polymeric films with
appropriate gas permeability to create a desired atmospheric
composition around and within the commodity. MAP is widely
used in marketing fresh-cut produce.
Applications of CAP & MAP to cut flowers are very limited
because decay caused by Botrytis cinerea is often a limiting fac-
tor to postharvest life, and fungistatic CO2 levels damage flower
petals and/or associated stem and leaves. Also, it is less expen-
sive to treat flowers with anti-ethylene chemicals than to use
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS
CA to minimize ethylene action. Commercial use of CA storage
is greatest on apples and pears worldwide; less on cabbages,
sweet onions, kiwifruits, avocados, persimmons, pomegranates,
and nuts and dried fruits, and vegetables. Atmospheric modifi-
cation during long-distance transport is used on apples, aspara-
gus, avocados, bananas, broccoli, cane berries, cherries, figs,
kiwifruits, mangos, melons, nectarines, peaches, pears, plums,
and strawberries. Continued technological developments to pro-
vide CA during transport and storage at a reasonable cost (pos-
itive benefit/cost ratio) are essential to greater applications on
fresh horticultural commodities and their products.
There is a continuing increase in the number of companies
that make polymeric films for packaging produce and in the use
of modified atmosphere packaging (MAP) systems at the pallet,
shipping container (plastic liner), and consumer package levels.
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The greatest use of MAP (usually to maintain 2 to 5% O2 and 8
to 12% CO2) is on fresh-cut vegetable and fruit products. Use
of absorbers of ethylene, carbon dioxide, oxygen, and/or water
vapor as part of MAP is increasing. Although much research
has been done on use of surface coatings to modify the inter-
nal atmosphere within the commodity, commercial applications
are still very limited due to the inherent biological variability
of the commodity. Commercial use of CA during storage and
transport is greatest on apples and pears, less on kiwifruits, av-
ocados, persimmons, pomegranates, and nuts and dried prod-
ucts. Atmospheric modification during long distance transport
is used on apples, avocados, bananas, blueberries, cherries, figs,
kiwifruits, mangoes, nectarines, peaches, pears, plums, raspber-
ries, and strawberries.
Continued technological developments in the future to pro-
vide CA during transport and storage at reasonable cost (positive
benefit/cost ratio) are essential to expanded application on fresh
fruits and vegetables. The reduction in the handling losses and
the increased shelf life compensates for the higher technology
cost. Besides, the installation for CA or MA packaging is very
versatile, in the sense that they can be widely used for any fruit
and vegetable produce through out the year. This is an additional
advantage, which takes care of the capital cost. The major op-
erating cost is in the retention of temperature and hence will be
very low for western and European countries, as most part of the
year the temperature will be low. However, in the tropical coun-
tries this cost will be slightly higher. Hence, only value added
products like capsicum, apples, and mangoes are stored in CAP
or MAP.
METHODS OF ATMOSPHERE MODIfiCATION
IN PACKAGED FOODS
Low Oxygen Atmosphere by Vacuum
Vacuum Packing (VP)
The product is placed in a pack of low oxygen permeability,
air is evacuated and the package sealed. Since it is not possible
431
to evacuate all the air (∼0.3–3% may remain after sealing), as
discussed earlier (Fig. 1) the gaseous atmosphere of the vacuum
package is likely to change during storage (owing to microbial
and product metabolism, and gas permeation) and therefore the
atmosphere becomes modified. The earliest form of modified
atmosphere packaging developed commercially and still exten-
sively used for such products as primal cuts of fresh red meat,
cured meats, hard cheeses and ground coffee. It is not suitable
for soft products or bakery products since the vacuum process
causes irreversible deformation of the products. The process in-
volves packaging the product in film of low oxygen permeability
and sealing it after first evacuating the air. Under good vacuum
conditions the oxygen level is reduced to less than 1%. Due to the
barrier properties of the film used, entry of oxygen from outside
is restricted. In the case of vacuum-packed meat, respiration of
the meat quickly consumes the residual oxygen replacing it with
carbon dioxide, which eventually increases to 10–20% within
the package. Vacuum-packaged meat is unsuitable for the retail
market because the depletion of oxygen coupled with the low
oxygen permeability of the packaging film changes the color of
meat from red to brown due to the conversion of myoglobin to
metmyoglobin. This is not an acceptable color to the consumer.
A further disadvantage is the accumulation of drip during pro-
longed storage of meat in vacuum packs.
Vacuum Skin Packing (VSP)
Vacuum skin methods involve draping a softened film over
the product and applying a vacuum to form a skin. This allows
the vacuum packing of delicate products that would normally be
crushed under vacuum, and also of products that would puncture
vacuum films, such as lobsters.
Hypobaric Storage
Hypobaric or low-pressure storage is another form where
pressure, temperature and humidity are accurately controlled. It
has been used for the storage of soft fruits.
Gas Exchange Preservation (GEP)
Gas exchange preservation involves pumping air out of the
pack and replacing it with a series of gases, each with a dif-
ferent role, in quick succession (Church and Wood, 1992). CO
is added first to inhibit enzymes, followed by SO2 or ethylene
oxide to kill microorganisms, and finally N2 to flush out the
pack. While the initial investigations showed promising results,
further work on GEP has been suspended since, because of the
lethal and corrosive nature of some of the gases used, it was con-
sidered unlikely that such a system would gain worldwide regu-
latory approval. However, its use as a food-processing aid, rather
than a packaging technique, may warrant further investigation.
For instance, the HYPAZ Company’s (Vancouver, Canada) ster-
ilization process uses pure O2 under pressure (200 kPa) to
 432 K. SANJEEV AND M. N. RAMESH
kill microorganisms in both whole shell eggs and liquid egg
(Dennis, 1994). Cooking in atmospheres rich in H2 might offer
a means of minimizing heat treatments, since H2 accelerates
the thermal inactivation of Clostridium botulinum spores (Kihm
et al., 1990).
Preservation and shelf life extension of foods by means of
gas exchange has the potential for substantial energy savings
compared to preservation by heat exchange. The process con-
sists of the replacement of intra-tissue gases in particulate raw
foods with one or more gases, in appropriate sequence that will
stabilize or at least significantly extend the “like-fresh” shelf
life of the foods at ambient and/or chilled temperatures. The
process may be considered in some ways as an extension of
controlled-atmosphere (CA) storage, with certain differences.
One difference is that the effect of changing the atmosphere on
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extending the shelf life is accomplished in a matter of minutes
rather than over a longer period of time, as with CA storage. The
process uses gases other than oxygen (O2 ) and carbon dioxide
(CO2 ) that are specifically inhibitory to the activity of endoge-
nous or exogenous enzymes. Only the edible portion of the plant
or animal is processed and packaged, and the inedible waste is
left at the processing plant for by-product utilization. Storage of
the packaged products may be at ambient temperature as well
as at low temperature.
Gaseous Sterilization
Gaseous sterilization is a specialized type of chemical ster-
ilization where the gaseous chemicals are used. This has been
applied in the treatment of a variety of non food materials (Kaye,
1949; Phillips, 1957), such as plastics, leather, certain biologi-
cal products and delicate laboratory instruments. The intriguing
advantages of such a system are its simplicity in operation since
a gas distributes itself freely throughout an enclosed space, its
relatively high power of penetration, and avoidance of a wa-
ter soaked appearance, damage to heat sensitive materials, and
relatively easy removal of excess disinfectant by airing or evacu-
ation. With this technique, sterilization at ambient temperatures
can be achieved (Kramer et al., 1968). Cotton et al. (1928) were
the first to report the use of ethylene oxide as a fumigant. Practi-
cal sterility of dry foodstuffs, i.e., spices, grains and the like, has
been obtained by the use of ethylene oxide (Heath, 1964). This
gas is truly bactericidal in its action through alkylation of one
or more of the nitrogen atoms in the DNA bases of the microor-
ganisms, subsequently causing anomalies in the base pairing in
the DNA helix (Rose, 1965). It penetrates plant tissues readily
and has a broad spectrum of activity.
Gas Packaging by Mechanical Air Replacement
The desired headspace atmosphere in a modified atmosphere
pack can be achieved in two fundamental ways. These are the
replacement of air with a gas or gas mixture mechanically or by
generating the atmosphere within the package either passively
as in the case of fruit and vegetable or actively by using suit-
able atmosphere modifiers such as oxygen absorbents. There
are two different techniques for mechanical air replacement in
a package.
Gas Flushing
The gas-flush process is usually performed on a form-fill-seal
machine. A continuous stream of gas is injected into the package
to replace the air. This dilutes the air in the headspace surround-
ing the food product. When most of the air has been replaced the
package is sealed. There is a limit to the efficiency of this system
since replacement of the air in the package is accomplished by
dilution. Typical residual oxygen levels in gas-flushed packs are
2–5% oxygen. This means that the gas-flush technique is not
suitable for packaging very oxygen sensitive foods. The great
advantage of the gas-flush process is speed since it is a con-
tinuous operation. Flushing with nitrogen has been introduced
to extend the shelf life of beverages. A drop of liquid nitrogen
is injected into cans containing beer or carbonated soft drinks
immediately before seaming. The liquid nitrogen rapidly evap-
orates into gas, flushing out oxygen taken up during the filling
process. The benefits of flushing cans with nitrogen include in-
creased shelf life, retention of product aroma, and reduced can
corrosion.
Gas Flushing with Compensated Vacuum
The compensated vacuum process first applies a vacuum to
remove the air from inside a preformed or thermoformed con-
tainer holding the food and then introduces the desired gas or
gas mixture via lances or ports. Machines designed to perform
this operation are of the chamber variety. Since this is a two-
stage process the speed of operation of the equipment is slower
than the gas-flushing technique. Because the air is removed by
vacuum, however, the efficiency of the process with respect to
residual air levels is much superior.
MICROBIOLOGY OF GAS PACKAGING
Microbial Spoilage
Gram-negative bacteria are generally more sensitive to CO2
than are Gram-positive bacteria (Reddy and Amstrong, 1992).
In chill-stored proteinaceous foods such as meat and fish,
this generally results in the inhibition of the Gram-negative
Pseudomonas spp., Enterobacteriaceae, Acinetobacter spp., and
Moraxella spp., while the Gram-positive lactic acid bacteria and
Brochothrix thermosphacta instead become the dominant organ-
isms. As moulds have an absolute requirement for O2, packaging
in an anaerobic modified atmosphere can be extremely success-
ful in extending the shelf life of foods for which mould spoilage
is the major concern, such as bakery products or hard cheeses.
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS
If CO2 is used to produce the modified atmosphere, there is also
the additional benefit of the antibacterial and anti-mould activity
of CO2 . However, there is concern that the increased shelf life
may give rise to safety problems, as discussed below.
Microbial Safety—Clostridium Botulinum
Most of the research on MAP products has concentrated on
the extension of product shelf life. Concerns have been expressed
as far back as 1933, and also by regulatory authorities and food
industry groups (The National Food Processors Association,
Washington, DC, USA) that MAP may represent an undue safety
hazard for certain products (Church, 1993). It has been suggested
that the suppression of spoilage microflora might result in prod-
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ucts containing large numbers of pathogenic microorganisms
or toxin while still appearing to be organoleptically accept-
able (Thatcher et al., 1962). Historically, the non-proteolytic,
psychrotrophic strains of Cl. botulinum have been the major
safety concern. These strains can grow and produce toxin with-
out producing overt signs of spoilage. Fish and fish products
have been the greatest cause for concern with respect to Cl.
botulinum growth in MAP products. Hence, the US National
Academy of Sciences has recommended that fish should not
be packed under modified atmospheres until the safety of the
system has been established (Davis, 1993). The concern results
from the fact that all strains of Cl. botulinum are found in ma-
rine environments, and although the distribution varies greatly
with the geographic location and season, it is common enough
that fish processors must assume it is present (Goodburn et al.,
1988).
One approach that may provide the required safety with re-
spect to Cl. botulinum in MAP of fish is the use of a pre-
treatment step in combination with MAP. Potassium sorbate,
sodium chloride and irradiation have all been shown to be effec-
tive (Stammen et al., 1990). Since treatments such as potassium
sorbate dips, although effective, are not currently legal in the ma-
jority of countries involved in MAP, other possible safeguards
are the incorporation of time-temperature indicators or gas in-
dicators on packs to warn consumers of packs that have been
temperature abused (Davies, 1994). However, unless automatic
scanning technology is used to identify such products at the time
of sale, the effectiveness of indicator technology will be depen-
dent on the consumer noticing and following the advice given
by the indicator.
Other Pathogens
Concerns have been expressed about the ability of the
other psychrotrophic pathogens (e.g., Aeromonas, Listeria and
Yersinia spp.) to grow in MAP products (Anderson, 1990). The
studies with fish concentrated on cod (Gadhus morhua) and
rainbow trout (Oncorhynus mykiss), with storage at 0◦ C, 5◦ C,
and 12◦ C. In no instance was the growth/survival of any of the
433
pathogens examined (Listeria monocytogenes, Aeromonas spp.,
Yersinia enterocolitica and Salmonella typhimurium) greater un-
der MAP than in the aerobically stored control, and frequently
growth was reduced under MAP. The studies on meat concen-
trated on raw beef but also included cooked and dry-cured hams,
lamb, pork, chicken, and other poultry meat. With one excep-
tion, microbial growth/survival in MAP beef was never greater
than that in the vacuum-packed control, and occasionally growth
was reduced by using MAP. The one exception was verotoxi-
genic Escherichia coli (VTEC) on minced beef stored at 12◦ C, in
which growth was more rapid in one of the modified atmospheres
(80% O2 /20% CO2) examined than in the vacuum packed con-
trol, although its was slower that that in the aerobically stored
product. Pathogen growth was never greater in MAP ham than in
the vacuum-packed control, and was frequently reduced. Stud-
ies of pathogen growth/survival on MAP/VP lamb gave variable
results between replicates. Possibly as a result of pH differences
and/or bacteriocin production; however, MAP often decreased
pathogen growth/survival in lamb and poultry meat.
Overall results and the majority of those reported in the litera-
ture indicate that the risks from food borne pathogens in MAP are
no greater and are frequently less than those from aerobically
stored foods. These finding are substantiated by the excellent
safety record, to date, of MAP (Church, 1993). As is the case of
almost all aspects of food production, the hazard analysis and
critical control points (HACCP) system is likely to play a major
role in ensuring the safety of MAP foods (Davies, 1994). For
products in which the removal of O2 could permit anaerobic
food pathogens to survive in the product, creating a safety haz-
ard, it is recommended that one or more of the following criteria
should be met (Day, 1990):
• aw (water activity) <0.92
• pH < 4.5
• Addition of sodium nitrite (level governed by legislation)
• Temperature maintained below +3◦ C
Effects on Pathogenic Microorganisms
Knowledge of the effects of modified atmospheres on food
pathogens is incomplete particularly for the emerging pathogens
such as Listeria monocytogenes and Yersinia enterolitica. High
levels of carbon dioxide have generally been found to have an
inhibitory effect on Staphylococcus aureus, Salmonella spp.,
Escherichia coli and Yersinia enterolitica. The degree of inhibi-
tion increases as temperature decreases (Hintlian and Hotchkiss,
1986). There are five food-borne pathogenic bacterial known
to be capable of growth below 5◦ C—Clostridium botulinum
types E, Listeria monocytogenes, Yersinia enterolitica, entero-
toxigenic Escherichia coli and Aeromonas hydrophilia. Four
others are capable of growth at temperatures just above 5◦ C—
Staphylococcus aureus, Vibrio paraharaemolyticus, Bacillus
cereus, and Salmonella species. Consequently the ability of
modified atmospheres to inhibit the growth of these organisms
 434 K. SANJEEV AND M. N. RAMESH

in foods under refrigerated storage is of vital importance. Fortu-
nately most of these organisms do not compete well with harm-
less bacteria such as the lactic acid bacteria which grow rapidly
if temperature abuse occurs. Because Listeria monocytogenes
is microaerophilic as well as being capable of low temperature
growth its potential importance in modified atmosphere packs
needs to be clearly established since it is a common contaminant
of vegetables and poultry. The main cause for concern however
is the possible growth of Clostridium botulinum Type E, being
both an anaerobe and low-temperature tolerant. Of particular
concern is the fact that it may grow and produce toxin on the
product before spoilage is detectable to the consumer (Kauter
et al., 1981; Genigeorgis, 1985; Post et al., 1985).
Conflicting results on the effect of modified atmospheres on
the growth and toxin production of Clostridium botulinum make
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application. The comparative physical properties for some of
the popular cryogens are given in Table 5.
Exposing the food materials to a cryogenic medium will cause
internal stress buildup, due to fast freezing rate and this internal
stress may lead to cracking or shattering. The cracking or shat-
tering under such conditions could be due to volumetric changes
associated with the water-ice phase transition and non-uniform
contraction of empty spaces in microstructures following solid-
ification (Kim and Hung, 1994).
Cryogenic Grinding of Spices and Other Food Materials
Cryogenic grinding is a method of powdering spices/herbs at
sub-zero temperatures ranging from minus 17 to minus 57◦ C.

it difficult to draw valid conclusions. However, storage at low
temperatures (below 3˚C) and atmospheres containing about 2%
oxygen should provide an adequate safeguard for products sus-
ceptible to contamination with Clostridium botulinum.
CRYOGENICS
The term “Cryogenics” is referred for “ultra low temperature”
in an abstract sense. The range differs from standards of a country
in particular. The National Bureau of Standards, UK, has defined
cryogenic temperature as −150◦ C and below. According to this
definition, liquid nitrogen (B.P. −196◦ C) would be in cryogenic
range whereas and carbon dioxide (B.P. −78◦ C) would not be
(Kim and Hung, 1994). However, cryogenics is defined as a
branch of engineering specializing in technical operations at
very low temperature about, −50◦ C to −160◦ C (Parker, 1984).
Popular Cryogens
Cryogenic fluids or cryogens are those, which boil at cryo-
genic temperature at atmospheric pressure. Many fluids, for ex-
ample, hydrogen, helium, nitrogen, oxygen, etc., exhibit this
property. Liquid nitrogen is the major cryogen used for food
The spices/herbs are frozen with liquid nitrogen, as they are
being ground. This process does not damage or alter the chem-
ical composition of the product in any way. Normal grinding
processes, which do not use a cooling system, can reach up to
90–95◦ C. These high temperatures can reduce volatile compo-
nents and heat-sensitive constituents in spices/herbs.
Grinding of spices is an important step in the process, as
it involves the loss of volatile oil and aroma present in them.
Generally, spices are ground either for direct use or for making
value added products like oleoresins or oils from them. Usually,
grinding facilitates the release of aroma/flavour principles and
better uniform mixing with food materials. At the same time, the
grinding of spices results in considerable loss of aroma as a result
of heat generated (40 to 95◦ C) during conventional grinding.
Since spices are valued for their aroma and flavour, prevention
of their losses assumes importance (Gopalakrishnan et al., 1991).
In large scale grinders where continuous grinding is undertaken,
gumming of grinder walls and sieves (Anon., 1962) results in
frequent stopping of mill for cleaning works and reduces the
grinding rate. Spices, which are fibrous, pose a problem while
grinding, consuming enormous energy. Food materials exposed
to cryogenic temperatures become more brittle and crisp, and as
such, grinding them is easier.
Grinding of spices in the presence of a cryogenic fluid is re-
ferred to as cryogenic or cryogrinding. The grinding of spices

Table 5 Physical properties of cryogens

Physical properties Hydrogen Argon Helium Nitrogen Oxygen

Molecular Weight 2.016 39.95 4.003 28.01 31.999

Boiling Point @ 1 atm (◦ C) −252.8 −185.9 −268.9 −195.8 −183
Freezing Point @ 1 atm (◦ C) −259.2 −189.4 −272.2 −210 −218.8
Critical Temperature (◦ C) −239.9 −122.4 −268 −146.9 −118.4
Critical Pressure (atm) 12.9 48.0 2.26 33.5 49.6
Density, Liquid @ B.P., 1 atm (g/m3 ) 67800 1400000 36200 808100 1141000
Density, Gas @ 20◦ C, 1 atm (g/m3 ) 83.76 1656.31 164.99 1161.34 1331.13
Specific Gravity, Gas (Air = 1) @ 20◦ C, 1 atm 0.0696 1.38 0.138 0.967 1.11
Specific Gravity, Liquid @ B.P., 1 atm 0.0710 1.40 0.125 0.808 1.14
Specific Volume @ 68◦ F (20◦ C), 1 atm (m3 /kg) 11.99 0.60 6.03 0.86 0.75
Latent Heat of Vaporization (kJ/kg. mole) 904.81 6522.10 81.17 5580.07 6824.48
Expansion Ratio, Liquid to Gas, B.P. to 20◦ C 1 to 848 1–840 1–754 1–694 1–860

Source: SAFE HANDLING OF CRYOGENS (http://www-safety.deas.harvard.edu/services/cryo general.html)

 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS
under cryogenic conditions causes less distortion in the natu-
ral composition than ambient grinding. In cryogenic grinding,
evaporation of liquid nitrogen quickly chills both the spice and
the grinder. Fibrous materials become brittle and crisp making
size reduction easy. The use of liquid nitrogen usually results in
a cubic particle with good product flow characteristics. Grinding
in the inert atmosphere reduces the risk of fire hazards and dust
explosion. There are definite advantages of cryogenic grinding
as compared to conventional grinding (Wistreich and Schafer,
1962; Anon., 1962; Pruthi, 1991; Murthy, 1995; Murthy,
2001).
The fat content of spices poses problems of temperature rise
and sieve clogging during grinding Due to this temperature rise,
spices lose a significant fraction of their volatile oil or flavour-
ing components. Therefore, a cryogenic grinding system was
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designed and developed to cool the spices before feeding to the
grinder and also maintain the cryogenic temperature in the grind-
ing zone (Sing and Goswami,1999). The main components of
the cryogenic grinding system are a precooler and grinder. The
precooler consists of a screw conveyor assembly, a compres-
sor, a liquid nitrogen dewar, and a power transmission unit. The
design considerations, calculations, and development of the pre-
cooler have been discussed in the paper. A commercially avail-
able grinder was adopted for this purpose. The tests conducted
on grinding of cumin seed revealed that it could be successfully
ground below the temperature of −70◦ C. Above this tempera-
ture, sieve clogging took place. The increase in grinding temper-
ature from −160◦ C to −70◦ C resulted in a significant increase
in particle size of the product and specific energy consump-
tion in grinding. A variation in volatile oil content was obtained
in the range of 3.30–3.26 ml/100 g with increasing tempera-
ture from −160◦ C to −70◦ C, but this variation was found to be
non-significant at 5% level.
Cryo-Milling of Nutmeg
McKee et al. (1993) have worked on nutmeg and reported
that cryogenic grinding tends to produce ground nutmeg with
more consistent results across batches than ambient or chilled
grinding. Further, cryogenic grinding gave a higher percentage
of oleoresin and improved antioxidant property. The first at-
tempt has been made in Japan on cryo-milling of nutmeg, which
is highly difficult to mill due to its very oily and sticky nature.
Milling temperatures tested were in the range from room tem-
perature (25◦ C) to −100◦ C and revolution rates of 30,000 rpm
and 5,000 rpm. A stamp mill was used to prepare a reference
sample. It was impossible to mill nutmeg at a temperature above
−20◦ C because of its highly sticky nature but it is easily milled at
temperatures below −40◦ C. Therefore, the efficiency of milling
of nutmeg depends mainly on the milling temperature. In or-
der to prevent the milled powder from sticking to the machine,
the milling should be done at low temperature when such oily
and sticky materials are milled. Composition of nutmeg milled
at various temperatures has however been identical, which
can be explained by the supposition that volatile components
435
are dissolved in nutmeg oil and their volatility became rather
lower.
Cryo-Milling of White Pepper
Cryo-milling of white pepper, which seems to be easily milled
and in which essential oil is apt to be influenced by heat, has
been successfully cryo-milled. Milling temperature tested var-
ied from room temperature (25◦ C) to −100◦ C and revolution
rates were 3,000 rpm and 5,000 rpm. A stamp mill was used
to prepare a reference sample. Unlike the milling of nutmeg,
the milling of white pepper was easily carried out at any tem-
perature tested but the essential oil content was clearly reduced
in the case of milling at room temperature, which seems to be
due to volatilization of some essential oil components. Below
0◦ C, however, no reduction of essential oil has been observed.
Therefore, it is concluded that the absorption of milling heat by
cooling is important in order to prevent volatilization of essential
oil (Murthy, 2001).
Cryo-Milling of Cardamom
Gopalakrishnan et al. (1991) have worked on cardamom and
reported that cryogenic grinding provided superior quality prod-
uct by preventing the loss of high volatile constituents during
grinding. There is a need to optimize the process parameters
viz., the ground material temperature, type of grinder, rpm of
the grinder, powder particle size, feed rate of the spice, and
coolant, type of cooling, etc., which give the best quality prod-
uct at minimum cost. These conditions are product specific and
depend on the physical characteristics of the spices.
Cryogenic Grinding of Herbs
A scientifically controlled study using four herbs was con-
ducted comparing cryogenic grinding methods with normal
grinding methods. The herbs tested included feverfew, gold-
enseal, valerian and echinacea. In all cases the cryogenically
ground herb contained greater amounts of the constituents tested.
Feverfew herb showed the greatest difference, with the cryogeni-
cally ground herb containing 21.8% higher levels of partheno-
lide, the primary active constituent. Valerian root showed an
18.7% increase in valerenic acid when cryogenically ground.
Goldenseal root showed a 16.4% increase in berberine and
10.7% increase in hydrastine. Lastly, Echinacea purpurea root
showed a 12.1% increase in total phenolic content in the cryo-
genically ground root. Test results were obtained by HPLC
(high performance liquid chromatography) methods. Cryogenic
grinding was shown to significantly affect active constituent lev-
els in herbs. Test results showed an average increase of 15.6%
in constituents tested in four medicinal herbs when they were
ground cryogenically. The range was 10.7% to 21.8%, indicating
that some herbs are affected more than others by the tempera-
tures at which they’re ground. (Frontier Natural Products Co-op.
http://www.frontiercoop.com/contact/index.htm)
 436 K. SANJEEV AND M. N. RAMESH
Table 6 Comparison of the spice volatile oil retention by ambient and
cryogenic grinding
Ambient grinding Cryogrinding Increase due to
Spice (m1/100 g) (m1/100 g) cryo grinding (%)
White pepper 1.95 3.19 64
Black pepper 2.21 3.09 40
Pimento 2.27 3.08 14
Mace 9.10 14.50 59
Cloves 11.50 16.50 43
Source: M/s Alphine, Germany.
Other Food Materials
Cryogenic grinding is also applicable to a wide variety of food
materials viz., cocoa and chocolate, vanilla-sugar, coconut, cof-
fee, tea, dehydrated meats, etc. It has been found that there is a
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large gain in flavor when vanilla-sugar is fine pulverized. The
product has interesting possibilities and advantages as a replace-
ment for liquid extract. Coconut can be ground to eliminate ob-
jectionable fibers, while improving its aroma and flavor as high
fat content gets solidified and fibers become brittle. This offers
applications in syrups, cakes, and confectionery. Ground cocoa
and chocolate retain their natural flavor and aroma. Cryoground
coffee appears to have long lasting freshness of particular inter-
est in instant-coffee processing (Wistreich and Schafer, 1962).
The comparison of spice volatile oil retention by ambient and
cryogenic grinding of different spices is indicated in Table 6.
Cryogenic Freezing
Different types of freezing systems using liquid nitrogen are
on-line freezer, spiral freezer, immersion or dip freezer, and
batch cabinet. Both positive and negative features of these sys-
tems have been discussed by Wilhoft (1987). The novel tech-
nique of freezing is “crusto freezing,” or “cryo-mechanical sys-
tem” wherein the liquid nitrogen is used for initial rapid freezing
of the crust and the food is then frozen slowly in a mechanical
system (George, 1993). This offers the advantages of both the
systems—the flexibility and other benefits of cryo-freezing sys-
tem together with the lower unit-cost factors of mechanical sys-
tems. This technique is more economical as existing mechanical
systems need not be replaced.
Miscellaneous Applications of Cryogenics
Packaging. Liquid nitrogen injection system can be used for
both pressurization and inerting.
In pressurization, a drop of liquid nitrogen is injected into a filled
can just before sealing. When the nitrogen expands, the can
gets pressurized, increasing its strength and stackability.
In inerting, LN2 is added to an empty container before filling.
The nitrogen, which expands to 700 times its original volume,
displaces oxygen from the packaging, increasing the shelf life
of the products. These systems are useful for the packaging
of oxygen-sensitive products such as coffee, sauces, olives,
and cooking oil.
Peeling of Fruits and Vegetables
Weaver et al. (1980) reported LN2 can be used for peeling
of fruits and vegetables. In this method, tomatoes are immersed
in liquid nitrogen for 5–15 seconds and then thawed in warm
water to loosen the peel. Since this method involves no cooking,
there is a removal of only skin tissue with very small amounts of
internal tomato pulp. Skin removal would be with a tissue loss
of about 5–8%. This technique can also be applied for peeling
of other fruits and vegetables.
Homogenization of Biological Tissue
Iyenger and Kasperek (1977) have introduced cryogenic ho-
mogenization (brittle fracture) technique for sample preparation
of biological materials wherein the tissue is ground at near liquid
nitrogen temperature in an oscillating ball mill of teflon. This
method eliminates the risk of contamination.
These applications have been detailed by Murthy (1995)
Limitations of the Cryogenic Technique
Cryogenic technology has the following limitations
1. Liquid nitrogen has to be either produced or purchased for
this purpose.
2. Operators are to be trained to store and handle liquid nitrogen
to avoid sever cold burns.
3. Investment on imported machinery is high, but can be reduced
by indigenous manufacture.
However, the increased quality can pay for the extra invest-
ment made.
Application of cryogenics in the food industry is in its in-
fancy. Adapting the latest techniques to spice processing for high
quality powders and products makes the product competitive in
the international market. Feasibility of cryogenic technique for
processing and preservation is to be established for large-scale
operations.
CARBON DIOXIDE IN THE FOOD INDUSTRY
The use and effect of Carbon Dioxide has already been men-
tioned and the uses of Carbon Dioxide in the Food Industry are
summarized below.
Carbonating of Water, Soft Drinks, Beer
The best-known and major application today for CO2 is the
carbonation of mineral waters, soft drinks, beers, etc. Carbon
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS
dioxide is responsible for the refreshing “bubbles” in such drinks
and affords protection against the growth of bacteria. Further-
more, CO2 is used in this industry as a propellant gas for empty-
ing tanks and as a shielding gas for preserving the drinks quality.
Chilling of Foodstuffs
Liquid CO2 can be used to chill or freeze foodstuffs such
as pastry, bakery products, shrimps, meat products, etc. By ex-
panding liquid CO2 to atmospheric pressure, it will turn into
snow (−79◦ C) and gas in equal portions. The snow provides
about 85% of the chilling effect by sublimation. The use of liq-
uid CO2 often needs to be combined with appropriate equipment
(freezing tunnels, snow hoods, etc.)
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Drinking Water Treatment
Modern water works use CO2 together with lime to raise the
hardness of drinking water, especially with soft surface waters.
At the right pH-level, the mentioned treatment allows the for-
mation of a protective surface layer in water-mains pipe, thus
avoiding corrosion and improving water quality.
Food Packaging
Due to its growth inhibiting effect on microorganisms, CO2
is also very commonly used as a shielding gas for the packaging
of foodstuffs, often in combination with nitrogen (Modified or
Controlled Atmosphere Packaging).
Slaughterhouses
In the past several years, CO2 has been used in slaughter-
houses for stunning of pigs instead of using conventional electri-
cal stunning. The use of CO2 offers a wide variety of advantages,
such as reduced animal stress, less injuries, etc., with a better
meat quality and yield as a result. For poultry, gas mixtures are
used.
Different Forms of Carbon Dioxide
Gaseous Carbon Dioxide
This is used to carbonate soft drinks, for pH control in water
treatment, in chemical processing as a food preservative, as an
inert “blanks” in chemical and food processing, and as a growth
stimulant for plant life.
Solid Carbon Dioxide
This is also called dry ice (Carboglace
), and is produced by
expanding liquid CO2 at atmospheric pressure. The expansion
437
results in the formation of equal portions of gas and CO2 snow.
The CO2 snow formed is compressed in extruders or presses
at high pressure, resulting in the manufacture of blocks or pel-
lets. This is used quite extensively to refrigerate dairy products,
meat products, frozen foods and other perishable foods while
in transit. It is also used as a cooling agent in many industrial
processes, such as grinding heat sensitive materials and, vacuum
cold straps. Most important features are
Dry ice temperature is −78.9◦ C
Heat vaporization: 645 kJ/kg (152 kcal/kg) at 0◦ C
Specific density is 1.56 kg/dm3
Dry ice sublimates at atmospheric pressure, leaving no residue
Dry ice also creates a protective, bacteriostatic atmosphere when
used with foodstuffs.
Normally, solid blocks of carbon dioxide weighing 22–27 kg
are wrapped in heavy kraft paper bags. They are stored
and shipped in insulated containers and storage boxes of
varying size. Extruded dry ice pellets are normally stored
and shipped in bulk or bags in insulated containers. (Source:
www.corpbrothers.com/productcgc/cardioxide.htm)
Ideally, the dry ice should slowly evaporate and the cool CO2
should fill the bottom of the bucket, displacing the warmer,
lighter atmosphere and pushing it out the top of the container.
One kg of dry ice will produce 100 L of carbon dioxide gas so
about 100 g 20 L is plenty. Do not move or shake the bucket
while the dry ice is sublimating.
Dry ice is extremely cold and can cause burns to the skin
by merely touching it. It evaporates into carbon dioxide
gas, which is why we want it. CO2 is not inherently dan-
gerous, but we should make sure the area we are pack-
ing is adequately ventilated so that escaping gas will not
build to a level dangerous enough to asphyxiate. (Source:
www.survival-center.com/foodfaq/ff17-co2.htm)
Liquid Carbon Dioxide
This is used as an expendable refrigerant for freezing and
chilling food products; for low temperature testing of aviation,
missile, and electronic components; for stimulation of all and gas
wells; for rubber tumbling; and for controlling chemical reac-
tions. Liquid carbon dioxide is also used as a fire-extinguishing
agent in portable and built-in fire-extinguishing systems.
CO2 is recovered form many different sources. It is obtained
as off-gases from fermentation processes, limestone kiln gases,
natural CO2 wells, combustion gases from coke ovens, burning
of natural gas and various oils, as well as gas streams from chem-
ical and petrochemical operations, CO2 is purified and liquefied
be at least seven different processes.
Enzyme Activity and Carbon Dioxide
Lipase exposed to CO2 (under atmospheric pressure)
treatment at different pH and temperature conditions showed
a decrease in enzyme activity. Inactivation was found to be
 438 K. SANJEEV AND M. N. RAMESH
highest as the temperature increased from 20 to 50◦ C at initial
pH of 7.15. About 85% of the initial activity of the enzyme is
lost at initial pH of 7.15 and 50◦ C. The faster drop in pH and
enzyme activity occurred within 5 minutes. Without CO2 no
significant change (p > 0.05) was observed in activity at the
highest temperature (50◦ C). The pH drop and loss in enzyme
activity were higher at initial pH of 8.20. No changes in enzyme
activity and pH were observed when N2 was applied instead of
CO2 . Studies using gel electrophoresis showed no differences in
protein patterns between CO2 -treated lipase solution (Fadiloglu
and Erkmen, 2002).
Lipolytic microorganisms often are in fatty foods. During
cold storage there is a great opportunity for psychotropic bacte-
ria to grow and produce lipases. Most thermal processing may
leave heat-stable lipolytic enzymes almost intact (Andersson
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et al., 1978). Surviving lipases then can influence food qual-
ity later on, especially at low temperatures, where the storage
stability of lipases is high. The thermo stability of microbial
lipase varies considerably among organisms. A D-value of 4.8
min at 150◦ C has been reported for lipase from Pseudomonas
fluorescens (Driessen and Stadhouders, 1974). Lipase from
Alcaligens viscolactis and Lactobacillus brevis was inactivated
completely after heat treatment at 90–92◦ C for 10s (Driessen
and Stadhouders, 1974) and at 71.7◦ C for 16s (Chander et al.,
1973), respectively.
An attempt has been made to apply high pressure treatment
that reduces microbial counts (Erkmen, 2000) and enzyme ac-
tivity. This also affects product functionality (Farr, 1990). Ef-
fects of high-pressure treatments on enzymes may be related to
reversible or irreversible changes in protein structure (Cheftel,
1992). However, loss of catalytic activity can differ depending
on the type of enzyme, the nature of substrates, the temper-
ature and length of processing. Owaga et al. (1990) reported
that neither pectinesterase nor peroxidase activity from man-
darin juice was completely inactivated after pressurization from
100 to 400 Mpa. Similar behavior was observed for polyphe-
nol oxidase (PPO) activity. In that case the degree of enzyme
inactivation varied depending on the type of fruit and vegetable
products studied (Knorr, 1995) and strong enzyme activation
could be observed in cell-free extracts (Anese et al., 1995).
Alternatively, an atmosphere modified with carbon dioxide
(CO2 ) has been used as a physical application to influence many
enzyme activities; as an example, the inactivation of PPO and
thus the prevention of discoloration in fruits and vegetables (Gee
and Brown, 1978). Retention of α-amylase, glucose oxidase,
lipase and catalase activity by supercritical fluid (SCF) using
CO2 has been studied (Taniguchi et al., 1987a)
Astringency Removal and Carbon Dioxide
Gore (1911) found that astringency could be removed from
persimmons (Diospyros kaki) by keeping them for 3–5 days in
an atmosphere with a high concentration of CO2 . Tarutani and
Manabe (1957) also found that astringency is removed when
persimmon fruit is kept 3–4 days in an atmosphere containing
78% CO2 . Gazit and Levy (1970) recognized two distinct stages
in the disappearance of astringency following treatment with
CO2 . The first stage is an inductive one in which fruit has to be
kept to a certain minimum period in CO2 atmosphere. Whereas
in the second stage the fruit actually loses its astringency but
can occur after removal from the CO2 atmosphere. The dura-
tion of time between fruit removal from the CO2 and complete
disappearance of astringency depends on the length of time the
fruit was in the CO2 atmosphere. The longer the latter period,
the shorter is the time required for complete disappearance of
astringency up to point where the fruit comes out of the CO2 in
a non astringent condition.
It was found that full induction occurred after 9 hr in CO2
atmosphere and thereafter astringency disappearance rate were
independent of CO2 presence. Induction was not complete in
fruit held for 6 hr in CO2 and as a result astringency disappeared
at a slower rate while the shorter treatment, 3 hr and less, was not
effective. These results may be explained by the assumption that
in the inductive stage CO2 induces a process in which a certain
astringency-removing substance is synthesized quantitatively.
Once present, the substance functions without the continued
presence of CO2 . The effectiveness of this process depends on
the length of time the fruit has been kept in CO2 . The 3-hr period
was apparently too short a time for completion of the process
or for production of a large enough quantity of the substance.
The lag period found in the 6-hr CO2 treatment was probably
due to the time required for the astringency-removing substance
to build up to a certain level before its activity commenced.
Prolonging the period of CO2 treatment increased the quantity
of substance formed and consequently led to a faster removal of
the astringency.
When the astringency-removing factor reaches a certain max-
imum, removal of astringency no longer depends on further
synthesis of the substance, and therefore prolonging the CO2
treatment beyond 9 hr in this particular case did not change the
rate of loss of astringency (Gazit and Adato,1972). It may be
assumed that the process mentioned above is connected with
anaerobic respiration since the products of alcoholic fermenta-
tion, e.g. acentaldehyde and ethanol, remove the astringency of
persimmons very efficiently (Gore, 1911; Tarutani and Manabe,
1957). Furthermore, the fact that a CO2 atmosphere is far more
effective than N2 (Tarutani and Manabe, 1957), indicates that
CO2 , apart from producing anaerobic conditions, has an addi-
tional specific function in the process described. Further work
is required to elucidate this function.
SUPERCRITICAL CARBON DIOXIDE
The supercritical state was first reported in 1822 by Baron
Gagniard de la Tour. Hannay and Hogarth (1879) later demon-
strated that supercritical fluids also possessed solvating power.
But not until over one hundred years later were supercritical tech-
niques widely used in analytical as well as on an industrial scale.
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS 439

Supercritical Fluids Table 7 Critical conditions for various supercritical solvents

Critical Critical
The supercritical state is achieved, when the temperature and Fluid temperature (K) pressure (bar)
the pressure of a substance is raised over its critical values. In the
Carbon dioxide 304.1 73.8
supercritical state the distinction between the liquid and the gas Ethane 305.4 48.8
phase has disappeared and the fluid can no longer be liquefied Ethylene 282.4 50.4
by raising the pressure nor can gas be formed on increasing Propane 369.8 42.5
the temperature. Thus, changing the pressure can easily control Propylene 364.9 46.0
Trifluoromethane (Fluoroform) 299.3 48.6
the physiochemical properties of a given fluid, such as density,
Chlorotrifluoromethane 302.0 38.7
diffusivity, dielectric constant and viscosity or the temperature Trichlorofluoromethane 471.2 44.1
without ever crossing phase boundaries. Ammonia 405.5 113.5
The dissolving power of a supercritical fluid depends on its Water 647.3 221.2
density, which, unlike that of liquid solvents, is highly adjustable Cyclohexane 553.5 40.7
n-Pentane 469.7 33.7
by changing pressure or temperature. Especially in the vicinity of
Toluene 591.8 41.0
the critical point a small isothermal raise in pressure increases
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the fluid density remarkably while the effect diminishes with
increasing distance from the critical values. Thus, the solvent
strength of a fluid can be controlled more easily than that of
a liquid solvent. On the other hand, a supercritical fluid has
a higher diffusion coefficient and lower viscosity and surface
tension than a liquid solvent, which leads to a more favorable
mass transfer. The close relationship between the fluid density
and its dissolving power and its favorable mass transfer proper-
ties makes supercritical fluids a useful processing medium for
extraction and separation techniques.
Solvents of Supercritical Fluid Extraction
Choice of SFE solvent is similar to regular extraction. The
principle considerations are
• Good solving property
• Inert to the product
• Easy separation from the product
• Cheap
• Low PC because of economic reasons
Carbon dioxide is the most commonly used SCF, due primarily to
its low critical parameters (31.1◦ C, 73.8 bar), low cost and non-
toxicity. However, several other SCFs have been used in both
commercial and development processes. The critical properties
of some commonly used SCFs are listed in Table 7.
Organic solvents are usually explosive so a SFE unit work-
ing with them should be explosion proof and this fact makes
the investment more expensive. The organic solvents are mainly
used in petrolchemistry. CFC-s are very good solvents in SFE
due to their high density, but the industrial use of chloro-fluoro
hydrocarbons are restricted because of their effect on the ozono-
sphere. Beside CO2 , water is the other increasingly applied sol-
vent. One of the unique properties of water is that, above its
critical point (374◦ C, 218 atm), it becomes an excellent solvent
for organic compounds and a very poor solvent for inorganic
salts. This property gives the chance for using the same solvent
to extract the inorganic and the organic component respectively.
(http://sunny.vemt.bme.hu/sfe/angol/index.htm)
Source: http://sunny.vemt.bme.hu/sfe/angol/index.htm.
There are a large number of compounds that can be used
as a fluid in supercritical techniques (Luque de Castro et al.,
1994), but by far the most widely used is carbon dioxide.
From the viewpoint of pharmaceutical, neutraceutical, and
food applications it is a good solvent, because it is non-toxic,
non-flammable, inexpensive, easy to remove from the product
and its critical temperature (Tc ) and pressure ( pc ) are relatively
low [Tc = 31.1◦ C, pc = 72 bar] (Luque de Castro et al., 1994).
These properties make it suitable for extracting, for example,
thermally labile and non-polar bioactive compounds but,
because of its non-polar nature, it cannot be used for dissolving
polar molecules. The solubility of polar compounds and the
selectivity of the process can be increased by adding small
quantities of other solvents (Entrainers), such as ethanol, in the
fluid. On one hand, it decreases the processing time, increases
yield and make it possible to use milder processing conditions,
but on the other, it complicates system thermodynamics and
increases capital costs. Further information concerning the fun-
damentals of supercritical fluids can be found in Fundamentals
of Supercritical Fluid by Clifford (1998).
Supercritical Fluid Extraction
A large number of books and articles describing different
supercritical applications, which utilize carbon dioxide as a su-
percritical fluid, have been published during the past decade.
After a sharp increase in the 1980s, the amount of patent appli-
cations has been more stable being around 100 applications per
year in the 1990s. The majority of the patents concentrate on
food, pharmaceutical, or chemical industry, although supercriti-
cal techniques have been successfully applied also in other areas
like environmental protection. By far the most often used super-
critical fluid technique is supercritical fluid extraction (SFE).
Evidently, most of the patents have never been industrial-
ized but in some areas, such as in decaffeination of coffee
(Zosel 1974, 1981) and tea (Vitzthum and Hubert, 1979; Gehrig
and Forster, 1990) and in processing of hops (Kruger, 1980),
the supercritical extraction has replaced the traditional solvent
 440 K. SANJEEV AND M. N. RAMESH
extraction methods. The other widely used industrial applica-
tions are tobacco extraction (Prasad and Grubbe, 1996), making
of spice extracts (Nguyen et al., 1992; Kerrola, 1994) and ex-
traction of fats and oils (Friedrich, 1984; King and List, 1996;
Zeidler et al., 1996).
A typical batch extraction proceeds as follows. Raw mate-
rial is charged in the extraction tank, which is equipped with
temperature controllers and pressure valves at both ends to keep
desired extraction conditions. The extraction tank is pressurized
with the fluid by means of pumps, which are also needed for the
circulation of the fluid in the system. From the tank the fluid and
the solubilized components are transferred to the separator(s),
where the solvation power of the fluid is decreased by increasing
the temperature, or more likely, decreasing the pressure of the
system. The product is then collected via a valve located in the
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lower part of the separator(s).
In the US, some very large extractors were made in the
1980s for extracting coffee, hops, and tobacco, the biggest being
over 40,000 L in volume. At the moment, the total amount of
industrial-scale extraction vessels (≥100 L) is globally around
125 L. The data was collected from Gehrig (1998), Uhde
Hochdrucktechnik GmbH and Chematur Ecoplanning Ltd.
Functional Applications
The various physical states of carbon dioxide at various tem-
peratures and pressures and those regions where a supercritical
process can perform functions applicable to food processing
is well reported (Brogle, 1982). The high pressure region is
generally used for processes where total extraction of a target
compound is desired, since most extractable compounds exhibit
their maximum solubility in a supercritical solvent at higher
pressure. Increasing the temperature at a given pressure has a
variable effect, and frequently there is a trade-off between ef-
ficiency and selectivity as a result of increased vapor pressure
with elevated temperature. In the operating region closest to the
critical point, the process becomes selective for the more soluble
components of a mixture. If a material containing components
of widely variable solubilities is loaded into the extraction ves-
sel, the low-pressure region can be suitable for crude separations
or deodorization. If an extraction is carried out over a range of
conditions, then a degree of selectivity can be introduced as the
process removes the components according to their relative sol-
ubilities, starting with the most soluble and progressing through
the components.
The various functions provided by SFE and specific examples
of food-related systems are.
Total Extraction
The objective of any simple extraction process is the removal
of a component, or group of related compounds, from an insol-
uble matrix. As discussed earlier, the solubility of a given solute
tends to increase with the operating pressure and temperature.
The practical limits or each parameter are governed by different
factors however. Temperature must be kept below a level where
the material being extracted begins to suffer thermal degrada-
tion. Pressure is more related to economic considerations, as
construction and operating costs increase with higher system
pressures in some cases, it has been shown that improvement of
extract quality or purity may be obtained with conditions that
are actually below those which result in highest solubility and
yield. For example, olive oil extracts obtained at maximum sol-
ubility tend to be darker and less appealing than those extracted
at slightly lower conditions (Brogle, 1982) and the natural pesti-
cide pyrethrin, extracted from Chrysanthemum blossoms (Sims,
1982). Given the lack of theoretical knowledge of phase equi-
libria in the supercritical region (Rizvi et al., 1986), it is under-
standable that each potential application of supercritical extrac-
tion becomes a search for those conditions that maximize yield
and quality of the targeted product, but still allow for safe and
economic operation of the system.
Deodorization
Rather than operating at maximum solubility, the tempera-
ture and pressure are maintained much closer to the critical point
of the solvent. Under these conditions, the more soluble compo-
nents, which are generally those associated with characteristic
odors of a substance, are preferentially removed from the mix-
ture. This type of process would be of use either to remove an
objectionable aromatic compound from a desired product or,
viewed in reverse, to extract desirable odor concentrates that
could be used as ingredients for a processed or engineered food.
Fractionation
When a supercritical process is carried out on a multicompo-
nent system over a range of conditions, some degree of selectiv-
ity can be introduced into the process. This characteristic can be
used to separate components, where there is sufficient difference
in their relative volatilities, or simply to concentrate the more
soluble components. One method of achieving fractionation is to
carry out a total extraction, then pass the loaded solvent through
a series of separation vessels where the temperature and/or pres-
sure conditions are changed in a stepwise fashion. This configu-
ration is sometimes referred to as multi-stage fractionation. The
result is that dissolved components drop out of the supercritical
solvent at the point in the system where they are no longer solu-
ble, and collect in the appropriate vessel. If the relative volatility
of the components is sufficiently different and the conditions
maintained in the separation vessels mirror those differences, a
high degree of separation is theoretically possible. In a mixture
of more closely related components, it may only be possible to
change the relative balance of the individual components in the
extract composition, when compared to that of the original mate-
rial. One drawback of such an approach is that the system is only
capable of separating the original mixture into as many fractions
as there are separation vessels. In addition, the engineering and
operation of the system become more complicated and costly, if
precise temperature and pressure differences must be maintained
in the extraction apparatus to achieve the desired products.
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS
Entrainers /Co–Solvents
Fractionation of a multicomponent system is one applica-
tion where the use of entrainers-compounds with intermediate
volatilities-and co-solvents can enhance the efficiency of the
separation. The addition of an entrainer to the primary solvent
has been found not only to increase total solubility but also to
increase the difference in the relative solubilities of the com-
ponents, thereby facilitating their selective recovery. Selection
and incorporation of an appropriate entertainer can decrease the
required temperature and pressure conditions, increase yields,
shorten process times, and increase the degree of fractionation
that can be achieved (Brunner et al., 1981).
Researchers and industrial R&D personnel have been study-
ing a different approach to fractionation. This approach involves
coupling an extraction system to columns designed to establish
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countercurrent rectification, or internal refluxing, as the sepa-
ration is taking place. Systems of this type route the loaded
supercritical solvent from the extraction vessel into a column
where an increasing temperature gradient has been established.
As dissolved components begin to condense within the column
and flow back towards the extraction vessel, they set up coun-
tercurrent flow against the rising loaded solvent. The result is
that the least soluble components are “washed out” of the rising
solvent flow and are concentrated in the extraction vessel, while
more soluble components are carried through the system to the
separation vessel.
By choosing suitable operating conditions at the beginning
of the extraction, then increasing pressure over the course of the
process, the components of the original mixture can be collected
as they elute from the system in order of relative solubility. The
feasibility of such as approach was first demonstrated by Zosel
(1978). Triglycerides of cod-liver oil were separated into 50 frac-
tions, each with an increasing molecular weight and degree of
unsaturation. In a subsequent experiment a mixture containing
equal proportions of C16, C18, and C20 fatty acids—compounds
were separated. These compounds were difficult to separate us-
ing existing techniques. The fractions recovered contained single
fatty acids with greater than 95% purity. A fractionation process
for the separation of a methyl ester mixture prepared from fish
oil into single fatty acid ester fractions with greater than 99% pu-
rity have been reported (Eisenbach, 1984). In view of the recent
interest in the therapeutic value of the ω-3 marine fatty acids,
such a process could conceivably be used to produce extracts for
food and pharmaceutical uses. A similar process could be em-
ployed in the fat and oil industries, where the fatty acid balance
in the product determines functional characteristics.
Extending for over two decades, the investigation of food-
processing applications for supercritical extraction of fraction-
ation has led to the identification of many possible uses. In a
few cases, the supercritical extraction processes have become a
commercial reality. Many more applications are believed to be
under development—or at least under consideration—by both
small and large companies. Although there is not a great deal
of information concerning supercritical processes that are under
study by commercial interests, removal of gums from soy oil for
441
lecithin recovery; extraction of oil from avocados; extraction
and deodorization of sunflower and rapeseed oils; extraction of
oils and flavors from fermented seaweed; and recovery of oil
from cottonseed, wheat, and sorghum are reported to be under
development (Morris, 1982). SFE has been successfully used
for two commercial applications.
Decaffeination of Coffee
The first commercial, and perhaps largest-volume, supercriti-
cal extraction process has been operating in Germany since 1978,
in the decaffeination of raw coffee beans. The process involves
first soaking the beans in water to make the supercritical CO2
more selective for caffeine. The presoaked beans are loaded into
the extraction vessel, and SC-CO2 is circulated through the sys-
tem, solubilizing the caffeine in the extraction vessel and trans-
ferring it to water in a scrubbing vessel. Although this approach
requires decompression and distillation of the water to ultimately
recover the caffeine, it eliminates the energy-intensive process
of depressurizing and represurizing the CO2 for solute recovery.
The system reportedly reduces caffeine from initial levels that
typically fall between 0.7 and 3% to less than 0.02%, without
affecting the characteristic flavor and aroma components. The
decaffeinated end product is indistinguishable from untreated
samples in its organoleptic properties (Zosel, 1981).
Several variations on the basic decaffeination process have
been patented since the process was first developed. Many of
these variations use activated carbon, rather than water, to ad-
sorb the dissolved caffeine from the supercritical solvent. Within
these variations the palletized carbon can be paned either in a
separate vessel or loaded directly into the extractor along with the
coffee beans. The latter configuration has the added advantage
of eliminating the solvent scrubbing vessel altogether, as well as
the need of circulating the supercritical solvent. In such a sys-
tem, the coffee beans and carbon pellets are mixed together and
then loaded into the extractor, such that the carbon occupies the
spaces between the beans. Once sealed, the extractor is charged
◦
with SC-CO2 at approximately 75 C and 180 atmospheres. The
carbon pellets adsorb the caffeine as it dissolves from the beans
(Zosel, 1981). When the extraction has progressed to the point
where the caffeine in the beans is reduced to the desired level,
the beans can be separated from the smaller carbon pellets by a
sieving operation. Although both refinements of the basic tech-
nique require additional processing to recover the caffeine from
the activated carbon, they still represent considerable energy
savings over having to manipulate the pressure of the solvent
stream for caffeine recovery.
Recovery of Hops Extracts
Also developed in Germany, the second food-related, com-
mercial supercritical process employs CO2 to obtain concen-
trated hops extracts. These extracts are used to give beer its
characteristics bitter flavor. The conventional extraction pro-
cess use liquid solvents, such as dichloromethane or methylene
 442 K. SANJEEV AND M. N. RAMESH

Table 8 Food applications for supercritical processing rapidly owing to the rapid vaporization of superheated steam
Process Raw material Reference and subsequently shrinks as a result of the vapors cooling (Fan
et al., 1994). The reaction of added bicarbonate with acids to
Decaffeination Coffee Zosel (1981b) generate CO2 , which accumulates in the nucleating sites, has
Tea Brunner et al. (1981)
Deodorization Vegetable Oils Zosel (1979)
been exploited to help increase the expansion further (Lai et
Animal fat and oil Zosel (1979) al., 1999). Although subcritical CO2 , can be used to puff ce-
Brewer’s yeast Eisenbach (1980) real melts at lower temperatures, the limited solubility of CO2
Aroma recovery Spices Vitzthum and Ilubert (1980) at low pressures limits the quantity of gas that can be added
Ilops Vollbrecht (1982) before process instabilities are encountered. The problems as-
Tobacco Hubert and Vitzthum (1978)
Coffee Roselius et al. (1982)
sociated with the gases in the melt may also cause problems in
Apples Schultz et al. (1967) obtaining a uniform cell structure. In addition, subcritical CO2
Oil recovery Soy beans Friedrich and List (1982) cannot be used as a solvent for adding ingredients within the
Peanuts Stahl et al. (1978) extruder.
Sunflower Eggers and Tschiersch (1978) The combination of extrusion processes and supercritical
Rapeseed Eggers and Tschiersch (1978)
Corn germ Christianson et al. (1982)
fluid technology, which both require high pressures, provides an
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Coconut Stahl et al. (1978) elegant means to overcome most of the shortcomings of the con-
Cocoa Irani and Funk (1977) ventional extrusion process and the subcritical CO2 processes.
Lemon Anon (1984) Supercritical fluid extrusion (SCFX) involves the introduction
Olives Zosel (1982) of a supercritical fluid, preferably CO2 , carrying fluid-phase-
Oil refining Fatty acid removal Maddocks and Gibson (1977)
Hydrogenation Kershaw (1977)
soluble micronutrients, flavorants and colorants, into a cooked
Scparation Gangoli and Thodos (1977) (gelatinized), if necessary, cooled (below 100◦ C) melt contained
Fractionation Cod liver oil Zosel (1978) within an extruder of modified configuration.
Fatty acid esters Peter and Brunner (1978)
Glyceride mixtures Panzer et al. (1978)
Design Considerations

chloride, to distill the desirable hops resins. Subsequent evapo-
ration of the solvents is required to reduce their residual levels
to below those mandated by regulations. By contrast, in SFE,
the resins are dissolved in supercritical CO2 , and then easily
recovered in a solvent free state by reducing pressure.
In the SFE process, the milled hops are formed into pellets to
crush the substructures of the grain that contain desirable resins
and to make them more accessible to the solvent (Gardner, 1982).
The pellets are then batch-loaded into the extractor, and carbon
dioxide is passed through them. Single-stage pressure reduction
of the solvent stream yields a yellow-green, pasty extract, which
contains 99% of the desired resins contained in the raw hops
(Hubert and Vitzthum, 1978). The supercritical hops extraction
process has been reported to be more costly to operate than
conventional solvent processes. Also, industry sources state that,
while the supercritical hops extracts are thought to be of higher
quality with a richer, fuller aroma, they do not command a higher
price from brewers (Harold and Clerke, 1979). The process,
however, eliminates the need for methylene chloride a suspected
potential carcinogen that faces increasing restrictions on its use
(Basta, 1985). A summary of Food applications of SCFE are
indicated in Table 8.
The concept and design considerations for the extrusion pro-
cessing of foods utilizing the SCFX principles for the production
of macro-to microcellular structures with unique physicochem-
ical, sensory and textural attributes are similar to those sug-
gested for the production of plastic foams (Park et al., 1992).
The specifics of the concept are broken down into the following
four major successive steps.
1. Development of gas-holding rheological properties by mix-
ing alone or by cooking (gelatinization), mixing and cooling,
if necessary, to less than 100◦ C, as in starch melts.
2. The injection of SC-CO2 possibly loaded with solutes, into
the dough or melt at a rate not exceeding the saturation limit,
and mixing to create a single phase within the extruder barrel.
3. The creation of a controlled thermodynamic instability by
manipulating the pressure and/or temperature in the extruder
to induce and control bubble nucleation rates.
4. The control of the degree of cell growth during the setting of
the product structure through appropriate die selection and
post-extrusion drying and cooling processes.
The specific process design requires experimental studies to be
carried out on all four steps.

Supercritical Fluid Extrusion (SCFX)

Gas injection, in general, offers the possibility of low-
temperature puffing. Several researchers have explained the phe-
nomena involved in the steam-puffing process (Ferdinand et al.,
1990; Fan et al., 1994; Lai et al., 1999). The extrudate expands
Applications
Generally, the SCFX process has the potential to offer addi-
tional flexibility and opportunities wherever extrusion process-
ing is currently being used. A major issue in the use of con-
tinuous extrusion processing versus batch extrusion processing
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS
is the inabilities to optimize simultaneously each unit opera-
tion that occurs within the extruder. For example, only a single
screw speed can be used, although high screw speeds are de-
sirable for cooking, whereas slower speeds are desirable for
cooling. The introduction of high mechanical energy into the
melt has been shown to produce low density products with
higher water solubility indexes (Kirby et al., 1988). Thus, ex-
trusion processes often represent a compromise between the
high temperatures needed for low densities and the lower shear
needed to preserve the starch-water interactions that govern both
mouth feel and texture. The ability to puff products with gases
at low temperature is therefore very appealing for many types
of products. A derivative advantage of SC-CO2 -based puffing
includes CO2 - filled pores at the exclusion of oxygen and its
deleterious effects on product quality. Some of the specific ar-
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eas that go beyond those reported earlier (Mulvaney and Rizvi,
1993), and in which some have conducted feasibility studies
are:
Breakfast Cereals. A good ready-to-eat (RTE) breakfast ce-
real might be characterized as having a low density, tender tex-
ture or bite, and a long bowl life. Although continuous extrusion
processes are no doubt used to manufacture some RTE break-
fast cereals, a patent (Efstathiou, 1993) reveals that multi-step
gun-puffing processes are still used. In this case β-carotene and
other vitamins were mixed into a cooked and cooled cereal of
appropriate moisture content. The mixture was then formed into
discrete pieces, and dried and puffed into RTE cereal pieces. In
an SCFX version of this process, SC-CO2 could be used to di-
rectly deposit the β-Carotene into the cooked and cooled melt.
Upon exiting the die, CO2 gas would puff the product, which
would then have to be dried or toasted to obtain the final product.
Final densities as low as 0.16 g/cm3 for a cornmeal-based cereal
formula using the continuous process can be obtained, which
are acceptable for RTE breakfast cereals. Other possibilities in-
clude the microstructuring of flakes to improve the tenderness
of extruded flakes.
Pasta. Quick cooking pasta can be obtained by microstruc-
turing an otherwise traditionally prepared pasta product: one
that has not been pre-cooked. The SCFX process was used to in-
ject SC-CO2 into uncooked semolina pasta using a short-barrel
version of the SCFX process. This process was aided by the
fact that pasta extrusion is an inherently high-pressure and low-
temperature process so as not to denature the flour proteins.
The porosity and/or CO2 interactions result in the lightening of
the product color. More the SC-CO2 was injected, lighter the
product. This phenomenon has been observed for puffing using
nitrogen gas (De Almelda, 1993).
Enzyme Activity and SC-CO2
To develop other new fields where SC-CO2 extraction is avail-
able, the applications of SC-CO2 to remove organic solvents
from antibiotics (Kamihira et al., 1987), the preparation of de-
fatted rice-koji without decreasing several enzymatic activities
443
for solubilizing and saccharifying steamed rice (Tokuda et al.,
1986) and the extraction of vegetable oils have been studied.
Investigation was done to see the effect of SC-CO2 on several
enzymatic activities in order to elucidate whether SC-CO2 fluid
could be widely applied to adjust enzymatic activities in a large
number of natural products.
The exposure of an enzyme preparation to SC-CO2 causes a
decrease in enzymatic activities. Treatment with SC-CO2 is ex-
pected to make it possible to denature undesired enzymes such
as those associated with the oxidation of lipids. As an example,
Christianson et al. (1984) have shown that peroxidase activity in
corn germ flour defatted with SC-CO2 was decreased to 1/10th
as compared with that in hexane-extracted corn germ flour.
Taniguchi et al. (1987b), reported the removal of lipids form
rice-koji (Tokuda et al., 1986) and mustard seeds (Taniguchi
et al., 1987b) by extracting with SC-CO2 .
In certain applications enzymes are not inactivated by treat-
ment with SC-CO2 . Randolph et al., (1985) and Nakamura et al.
(1985) found that SC-CO2 can function as a medium for en-
zymatic reactions. Hence, SC-CO2 may be used not only as
a powerful solvent for extracting substances from natural prod-
ucts with thermally unstable enzymes, but also as a non-aqueous
medium available for enzymatic reactions instead of organic
solvents.
Supercritical Fluid Chromatography
In addition to the supercritical extraction methods, the su-
percritical fluid chromatography (SFC) is another supercritical
technology that has been commonly used. SFC as a processing
tool can be considered as a variation of a typical liquid chro-
matographic separation, where fluid replaces liquid eluent, or as
an SFE process, where an additional solid phase is added to the
SFE vessel. The fluid can flow concurrently or counter currently
with the feed flow depending upon the nature of feed and target
compound. The instrumentation is very similar to that used in
the SFE processes, except there is a need for a device by which
the feed is added to the fluid stream. The raw material can be
added either constantly or in batches, for example, by injection.
The packing of a SFC column can consist of an inert material
such as steel rings or typical chromatographic packing materials
(e.g., silica or C18). SFC is utilized as an analytical technique
rather than a processing tool. It has been used in the food and
pharmaceuticals industries for the quality analysis, where heat-
labile non-volatile components need to be quantitated (Chester
et al., 1998). Supercritical carbon dioxide is a rather non-polar
solvent. Thus, those stationary phases that are used with non-
polar solvents in liquid chromatography (LC) are the most fea-
sible for SFC applications. Replacing LC methods by SFC has
advantages
Decreases analysis time
Increases sample throughput
Decreases liquid waste
 444 K. SANJEEV AND M. N. RAMESH
New Applications of SC-CO2
Supercritical Particle Formation
In the 1970s and 1980s, supercritical processes were mainly
focused on extraction and separation but, within the last 20 years,
interest in supercritical fluid processing has arisen in other areas.
Impregnation with supercritical solutions (Alessi et al., 1998),
reactions in supercritical fluids (Poliakoff and George, 1998;
Jessop, 1999), micro encapsulation (Castor and Chu, 1998) and
supercritical particle formation, to mention only a few appli-
cations, has attracted great interest lately. The importance of
homogenous microparticles has grown, as there is an increas-
ing need for their usage in different industries. Yet the currently
used microparticle-formation techniques, such as recrystalliza-
tion from liquid antisolvents, spray drying, milling, grinding,
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and lyophilization cannot be used to produce, for instance, cer-
tain pharmaceutical, dye, or explosive particles. The problems
of these techniques are large particle size distribution, solvent
residues in the products, high cost, excessive processing time and
damage caused by mechanical milling. Due to these defects, the
interest in more “gentle” supercritical techniques has increased.
The rapid expansion of supercritical solutions (RESS) technique
(Turk, 1999) and supercritical antisolvent crystallization have
proven their value in pharmaceutical particle formation.
Rapid Expansions of Supercritical Solutions (RESS)
The dissolving power of supercritical fluids depends on their
density. As the compressibility of the fluid near the critical point
is remarkable, the dissolving power of the fluid can be adjusted
to match either that of a gas or liquid solvent with minor modi-
fications in pressure. When the pressure drops, the supercritical
fluid expands which, in turn, decreases the dissolving power and
causes precipitation of components dissolved in the fluid. Very
rapid pressure decrease (<10−5 ), or fluid volume increase results
in immediate homogenous super saturation of the fluid which, in
turn, enables the formation of micro particles of uniform quality
(Debenedetti et al., 1993).
Basic Principle. The compound to be crystallized is dis-
solved in the supercritical fluid in the extraction chamber at
a certain pressure and temperature. The supercritical fluid is de-
livered to the precipitation chamber via a nozzle, the purpose of
which is to create as rapid and fine a spray of solvent as possible.
Since the pressure before the nozzle is considerably higher than
in the precipitation chamber, the fluid supersaturates immedi-
ately upon reaching the precipitation chamber. As a result of the
super saturation the compound precipitates in the bottom of the
chamber. Since the RESS technique is based on the use of car-
bon dioxide as the solvent for crystallization, the end products
are free of solvent residues. The most serious limitation of the
RESS technique is that under the most common processing con-
ditions (35–75◦ C; 100–400 bar) the solubility of polar or high
molecular weight compounds is rather low.
Supercritical Antisolvent Precipitation
The RESS technique is suitable for the crystallization of non-
polar compounds soluble in carbon dioxide. There are, however,
several bioactive and pharmaceutical compounds that are polar
and, therefore, dissolve better in the more polar organic sol-
vents. In the supercritical antisolvent crystallization technique,
the fact that the compounds do not dissolve in the supercriti-
cal fluid has been taken advantage of. The compound that is to
be crystallized is dissolved in an organic solvent, which under
the crystallization conditions also dissolves in the supercritical
CO2. The crystallization is achieved by adding the carbon diox-
ide fluid into the organic solvent, thus decreasing the density of
the solvent phase and enabling the crystallization of the target
compound.
The crystallization process can be achieved using two differ-
ent types of methods.
1. In the gas antisolvent (GAS) (Krukonis et al., 1994) method,
the compound dissolved in the organic solvent is simply
blended into the supercritical CO2 by, for instance, bubbling
the solution with the fluid so that the solution expands and
the compound crystallizes.
2. The solution is sprayed through a nozzle into the SC-CO2
(precipitation with compressed antisolvent, PCA) (Luna-
Barcenas et al., 1995) either as a batch process or continu-
ously. The continuous process can be a concurrent, supercrit-
ical antisolvent (SAS) process (Yeo et al., 1993), or a coun-
tercurrent, aerosol solvent extraction system (ASES) (Bleich
et al., 1993), in which the SC-CO2 flows against the solution
spray. The terminology in the field is not quite defined yet,
so some discrepancies may occur in the use of terms.
In the spray process, particle formation is much faster than in the
GAS technique. In addition to the temperature and pressure, the
particle size and morphology depends also on the spray pattern,
the drop size of the spray, and the mass transfer between the
drops and supercritical carbon dioxide. The spray pattern and
the drop size are further dependent on the velocity of the spray
and the dimensions of the nozzle (Subramaniam et al., 1997).
Both in the RESS and in the supercritical antisolvent crystal-
lization techniques, the key factor is the nozzle through which
the mixture of the solvent and the compound to be crystallized
is sprayed.
Outlook for the Future
Capital costs of the technique itself are relatively high at
the beginning, as in SFE techniques. A few proceedings (Anon.,
1997; Perrut and Subra., 1999; Bertucco, 1999) gives a overview
of these aspects. It seems that these reports are limited to two
fields of food science. One is fractionation of essential oils of
various origins for better stability or more favorable profile of
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS
aromatic products (Anon., 1997); the other and most popular
application is the fractionation of different fat or oil-derived
components, such as fatty acid esters (Fleck et al., 1998) and
steroids (Yeh et al., 1999). However, several patents may hinder
the utilization of new industrial SFC applications (Perrut, 1984;
McLachlan et al., 1991; Kleimann et al., 1991; Engelhardt, 1993;
Brunner and Reichmann, 1998).
A production-scale SFC application has been installed in
Europe for the fractionation of fish oil-derived fatty acid esters
(Engelhardt, 1993). In addition to the already patented com-
mercial uses, few other manufacturing-scale applications are
apparent at present, and published developments are rare. In
the future the most useful and routine applications may deal
with isolation and separation of highly valuable minor com-
ponents from the bulk. In these applications, even a prepar-
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ative scale SFC system can yield considerable amounts of
product.
Supercritical techniques are not yet very widely used in in-
dustry and based on the opinion of those involved it seems that
the field is in some kind of lag phase at the moment. However,
the diversity of the articles and the patents in the late 1990s indi-
cate that there is much interest in the utilization of supercritical
techniques in many areas. According to Perrut (1999), the four
aspects that we have to consider when we are trying to foresee
what will happen in the near future are
• Regulatory issues
• Quality considerations
• Innovative products
• Innovative processes
In recent years, the authorities have become more and more
aware of the environmental and occupational concerns of using
large amounts of toxic organic solvents. As a result, disposal
regulations have become stricter, which adds to processing costs
and, in many countries, most organic solvents have already been
banned in food processing (Perrut, 1999). Thus, there is pres-
sure to invent new, more environmentally safe processes. On the
other hand, the food industry, especially in Finland, has a strong
emphasis on added-value products such as high-value food addi-
tives, functional foods and nutraceuticals. In these the “natural,”
i.e. solvent-free preparation modes may add to market value of
a product. Although supercritical particle formation techniques
have not yet been very widely used in food applications, they
could be a useful tool in processing of nutraceuticals and func-
tional food ingredients in the future. The “gas” antisolvent pro-
cess has already been applied to, for example, the separation of
β-carotene (Chang et al., 1991). Supercritical fluid technologies
can also be applied in making new innovative products. One of
the very promising areas of research is microencapsulation of
drug molecules, which are used for controlled drug release in
the human body.
445
INERT GAS IN THE BEVERAGE INDUSTRY
The use of CO2 for carbonation of beverages is perhaps
one of its most widely recognized applications. In breweries,
CO2 is recovered as a byproduct of fermentation. It can then
be purified, compressed, and liquefied for further use in pack-
aging, tank counter pressure, carbonation, or the preparation
of dry ice blocks or pellets. Its many uses include (Source:
www.wittcold.com/techdocs/co2apps.htm).
Carbonation of beer, wine, soft drinks, and mineral water
Canned or bottled beverages for preservation during transporta-
tion and shelf storage
Tank pressurization in breweries and wineries
Blanketing of wines during bulk transport
Beer Foam
“Widget” in cans facilitates the nucleation of gas and pro-
motes foam generation during dispense (Bruning, 1994). Such
technology is allied to the use of nitrogen gas which, when
present in the range 10–30 ppm, enables far more stable foams
than obtained from carbon dioxide, which is typically present in
beers over the range 2000–6000 ppm (Carroll, 1979; Archibald,
1984).
Bubble Formation
Beer is supersaturated with carbon dioxide, but not to the
extent that it will spontaneously form bubbles against thermo-
dynamic energy barrier. Rather, bubble release is catalytically
promoted at nucleation sites, which may include cracks in the
container surface, insoluble particles, or gas pockets introduced
during dispense.
Mouth Feel
The inclusion of nitrogen in beer to improve foam also has the
impact of “smoothing” on the palate (Carroll, 1979). This may
be a direct phenomenon, but may also relate to the tendency of
beers containing nitrogen to have low carbonation, which will
cut down palate “prickle.” Langastaff et al. (1991) found that
dissolved CO2 correlated with foam volume and total CO2 .
INERT GAS IN THE DAIRY INDUSTRY
Inert gases are now being used by many agricultural pro-
cessing industries in Europe and North America as a simple
and efficient means of solving a number of manufacturing and
preservation problems. In the dairy industry, contact between the
 446 K. SANJEEV AND M. N. RAMESH
product and oxygen in the air can cause deterioration of nutri-
tive value and quality. Neutral gases such as nitrogen and carbon
dioxide are employed to prevent oxidation processes. Gases are
also being widely used in a number of milk processing appli-
cations such as drying operations, gas packaging of cheese and
milk powder, cream freezing, pH regulation of loctoserum, and
treatment of by-products and effluent. Some of these gas tech-
nologies are implemented in many countries by Mesco Liquid
Air’s parent company, Air Liquide, one of the largest world gas
producers (Faugeras, 1986).
Deoxygenation/Inerting
Injection of an inert gas (nitrogen) into the milk will eliminate
most of the dissolved oxygen. This can easily be done before
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processing or storage by fitting a small stainless steel sparger to
an existing milk pipeline. N2 is used because of its low water
solubility compared to oxygen (2.25 times less). The nitrogen
causes a modification of the physical equilibrium between the
gases dissolved in the milk, and the oxygen is automatically
desorbed. Depending on the efficiency required, the amount of
gas varies from 0.3 to 1 volume of gas per volume of milk. N2
can be used to homogenize the product stored in vats. Compared
with conventional mechanical mixing systems, the benefits of
nitrogen are no local heating of product, no risk of incorporating
air, and higher efficiency of mixing.
Gas Packaging
Gas packaging will extend the shelf life of dairy products by
3 to 4 times without the need for preservatives. Gas-packed milk
powder has a shelf life of more than six months, pressed cheese
about 60 days. Pressed cheese and milk powder are usually
packed with continuous “gas flushing” equipment that purges
air from the bag by continuous gas injection. A “compensated
vacuum” system is used for packing milk powder in tins; a vac-
uum is created inside the tins and then broken by injecting a gas
mixture just before setting the lid.
Whipped Cream
Whipped cream is stable foam, typically 25–30% by volume
of cream, and 70–75% of gas bubbles. The large number of fine
bubbles means there is a large contact area between gas and fat,
which can allow fat oxidation to take place. Using N2 rather
than air for whipping cream limits this oxidation. Injection of
nitrogen is very simple. It is injected under pressure through a
perforated plate in the base of the whipping bowl.
Milk Atomization
For milk powder production, dissolving CO2 in the milk be-
fore heating can increase the drying efficiency. As the milk is
ejected from the atomization disc the CO2 is released from solu-
tion, forming micro-bubbles within the droplets. This increases
the available evaporation surface, improving the transfer of heat
and water. As a result, savings in heat input are possible (in some
cases 10–15%). This method lowers the density of the final prod-
uct. Installation of a CO2 system in existing spray towers is very
straight forward, with minimal initial investment costs.
pH Regulation for Reverse Osmosis
Reverse osmosis is a technique that can be used to concentrate
milk-processing by-products by passing them through semi-
permeable membranes. However, certain components (e.g.,
phosphocalcic compounds) tend to precipitate and clog the
membranes. Lowering the pH can prevent this problem. CO2
can be used to temporarily lower the pH by 1 to 1.5 units. In the
case of lactoserum, the appropriate required concentration of
CO2 is about 1 g/litre. This technique gives the reverse osmosis
membranes an extended life.
Dairy Industry and Cryogenic Gases
When released to atmospheric pressure liquid N2 and
CO2 vaporize, consequently absorbing heat-both absorb about
80 kcal/kg (320 BTU/kg). This phenomenon is used for freezing,
cooling, and temperature control during processing.
CONCLUSION
There are a lot of potential applications of low oxygen and
inert gas processing in food industry, for improvement of the
product quality. It has widely been used in packaging and stor-
age of foods. Inert gas processing of foods has been adopted to
retain valuable nutrients by avoiding oxidation. Low oxygen or
Inert gas processing reduces the oxidative losses in foods. It also
retards the enzymatic browning by reducing the oxygen content.
There is still a gap on the information on the effect of a few of
the inert gases on spoilage and pathogenic microorganisms in
the environment of fresh plant food products and the removal
of residual gases and their effect on the browning enzyme sys-
tem. This indicates the need for further exploration in this area.
The use of liquid nitrogen as a cryogen has a significant role
in the food industry and has efficiently been adopted. But, data
on the cryogrinding of other spices needs to be made available
along with the economics of the process. Supercritical carbon
dioxide is used in various food processes for extraction, frac-
tionation, and deodorization. In case of decaffeination of coffee
and extraction of various volatile components, the role is quite
significant. Supercritical carbon dioxide has other roles in ex-
trusion and chromatography. Carbon dioxide has been used for
the packaging, storage, inerting, and enzyme activity. The gas
exchange process has the advantage that the effect of changing
 LOW OXYGEN AND INERT GAS PROCESSING OF FOODS
the atmosphere on extending the shelf life is accomplished in
a matter of minutes rather than over a longer period of time as
compared to CAP and MAP. Not much work has been done in
this area. By inert gas processing, in particular inert gas drying,
the retention of vitamin C and carotenoids can be increased. As
vitamin C is frequently used as an indicator of the quality of pro-
cessed products, a better retention of the vitamin C is indicative
of an improved quality of the dehydrated product. The effect
of inert atmosphere was significant in the case of retention of
vitamin C content. However, the economic feasibility of the pro-
cess has to be evaluated at the commercial scale. Further research
is needed to get a deeper insight into this process and to have
a better understanding of the physiological phenomena of ox-
idative component of the nutrient degradation. A lot of research
work has been carried out on inert gas packaging and storage.
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Not much research work has been carried out on inert gas pro-
cessing and pretreatment like blanching, cutting and drying etc.;
so, there is need for much research in this area. The effect of inert
gas processing of the steps like cutting, separating, blanching,
and drying, on the final product quality facilitates the selection
of suitable protocol for a comprehensive processing at the in-
dustrial level. More information is needed for CAP and MAP
storage with respect to economic feasibility of the process and
the process has to be evaluated at the commercial scale. Also
further research is needed in the retention of chlorophyll and
other pigments during processing using inert gas/low oxygen.
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