Semina
Semina
Semina
BY
INSTITUTE OF EDUCATION
IN AFFILIATION WITH DELTA STATE UNIVERSITY,
ABRAKA DELTA STATE.
Supervisor:
DR. INNOCENT OBUKOHWO
…………………………………….
ABSTRACT
Water activity is a crucial factor in determining the physical characteristics, processes, shelf
life, and sensory properties of foods. It is a thermodynamic property defined as the ratio of
vapor pressure of water in a system to the vapor pressure of pure water at the same temperature
or the equilibrium relative humidity of the air surrounding the system at the same temperature.
Water activity can be lowered or controlled by several methods, such as separating out of water
and adding solutes. Processes that can be used to remove water include drying, concentration,
dewatering by centrifuge, baking, extrusion, and frying. Solutes can be added to foods to reduce
water activity and improve functional and sensory properties. When only solutes are used to
reduce water activity, the specific antimicrobial effects and cost of solutes or humectants should
be considered for food product formulation. The sorption behavior of solutes is also a significant
factor in food product formulation. Water activity affects food spoilage, as moisture is necessary
for the growth of spoilage organisms. However, water activity is not the same as moisture
content. Moisture is necessary for the growth of bacteria, molds, and yeasts in sufficiently dried
foods
TABLE OF CONTENTS
INTRODUCTION
Conclusion
References
INTRODUCTION
Water is an important constituent of all foods. Why water activity and not water content? In the
middle of the nineteenth century, scientists began to discover the existence of a relation between
water in a food and its relative tendency to spoil. They also began to realize that the active water
could be much more important to the stability of food than the total amount of water present.
Scott [2017] clearly identified that water activity of a medium correlated well with the
deterioration of food stability due to the growth of microorganism. Thus, it was possible to
develop generalized rules or limits for the stability of foods by using water activity. This was the
main reason why food scientists started to emphasize water activity rather than water content.
Since then, the scientific community has explored the great significance of water activity in
determining the physical characteristics, processes, shelf life, and sensory properties of foods.
The water activity of fresh foods, as shown by Chirife and Fontan [2020], is 0.970–0.996. Other
applications of water activity are: (i) process design and control, (ii) ingredient selection, and (iii)
packaging selection. Water activity data are important to food processing, such as osmotic
dehydration and air drying. In drying operations, desorption isotherms at the process temperature
are needed for design and control purposes. The endpoint of drying or osmotic dehydration
process can be determined from the equilibrium moisture content. In the drying process, the
foods equilibrate with air equilibrium relative humidity; in osmotic or salting process, foods
equilibrate with the osmotic solution water activity. Hence, water activity plays an important role
in designing, operation, and control of drying processes and reverse osmosis. Water activity’s
depressing power of solutes needs to be considered when selecting ingredients or additives for
food product formulation. When food materials are packed in a semipermeable membrane, the
food will (a) collect moisture if its water activity is lower than the external relative humidity of
the air or (b) lose moisture if its water activity is higher than the relative humidity. The sorption
isotherm is necessary to predict the moisture transfer rate through the packaging film and edible
food coating, so that shelf life can be predicted.
The bacterial cell can only transfer nutrients in and waste materials out through the cell wall. The
materials, therefore, must be in soluble form to permeate the cell wall. A portion of the total
water content present in food is strongly bound to specific sites and does not act as a solvent.
These sites include the hydroxyl groups of polysaccharides, the carbonyl and amino groups of
proteins, and others on which water can be held by hydrogen bonding, by ion-dipole bonds, or by
other strong interactions. The binding action is referred to as the sorption behavior of the food.
The most successful method for studying the sorption properties of water in food products has
been the preparation of "Sorption Isotherms," or curves relating the partial pressure of water in
the food to its water content at constant temperature. The same practice is followed to study
curves relating water activity under equilibrium conditions to water content.
Two basic methods can be used to obtain the constant temperature sorption curves. In the first
method, food of known moisture content is allowed to come to equilibrium with a small
headspace in a tight enclosure and partial pressure of water activity is measured monometrically,
or relative humidity is measured using a hyqrometer. Water activity is equal to equilibrium
relative humidity divided by 100: (a w = ERH/100) where ERH is the equilibrium relative
humidity (%). Relative humidity sensors of great variety are available for this purpose, including
electric hygrometers, dewpoint cells, psychrometers, and others.
A second basic method for preparing isotherms is the exposure of a small sample of food to
various constant humidity atmospheres. After equilibrium is reached, the moisture content is
determined gravimetrically or by other methods. A number of saturated salt solutions are
available for this purpose. Saturated salt solutions have the advantage of maintaining a constant
humidity as long as the amount of salt present is above saturation level. Salt slushes and
solutions of glycerol or sulfuric acid are among those commonly used.
Knowledge of sorption behavior of food is useful in concentration and dehydration processes for
two reasons:
2. Water activity affects food stability and therefore it must be brought to a suitable level at
the conclusion of drying and maintained within an acceptable range of activity values
during storage.
Products containing free water give off moisture in vapor form to the air in the environment, only
when the vapor pressure in the air is below that of the product. The vapor pressure of a salt or
sugar solution is reduced in comparison to that of pure water. The amount of vapor in the
surrounding air generally is measured as relative humidity. At the equilibrium point, water is
neither given off nor absorbed. The vapor pressure of the food product then becomes identical to
that of the surrounding air.
However, water activity is not the same as moisture content. According to an article from the
University of California Davis, “Although moist foods are likely to have greater water activity
than are dry foods, this is not always so. ... Some foods with exactly the same moisture content
have quite different water activity.”
Water activity is the amount of free water that is available in food. It is a measurement of the
water that is not bound to components in the food such as sugar, salt or protein, and therefore is
available for microbial growth. Water activity is measured in values from 0.0 (bone dry) to 1.0
(pure distilled water). The lower the water activity value, the more “dry” a food item is
considered. The higher the water activity, the faster that microorganisms like bacteria, yeast and
mold will be able to grow.
Most pathogenic bacteria need a water activity of 0.90, while spoilage molds need at least 0.70
or higher for growth. Shelf-stable foods are below 0.85. For example, bread has a water activity
of about 0.95. Therefore, there is enough water available in bread to support mold growth, unless
preservatives are added. Crackers, on the other hand, have a water activity about 0.50, which is
too low, or dry, for mold growth.
Consider some ways that water activity applies to food preservation. It can be controlled by
adding salt or sugar to foods. Both salt and sugar work by binding with free water in the food
product so that water is no longer available to microorganisms for growth. Salt is more effective
at binding water than sugar. Think of the salt in pickles or in cured meat.
Water activity may also be decreased by removing water from the food product. Decreasing
water can be done by “cooking down” a recipe, which allows water to evaporate. Examples of
this are long-cooking jams and marmalades. Water can also be removed by dehydration as in
drying fruits, vegetables and meats (jerky).
Food Components
Protein and starch adsorb much more water at low water activities than do fatty materials or
crystalline substances like sugar. Pretreatment, such as heating, has little effect on proteins. On
the other hand, such pretreatment increases the amount of water-impenetrable crystalline starch
at the expense of amorphous starch. The smaller active site for adsorption means that less water
can be adsorbed Labuza [2017]. Sugars and salts present a difficult problem because the change
from an amorphous to a crystalline state occurs fairly rapidly at normal temperature Makower
[2015]. This change releases water, which may be picked up by other materials if the sugar is
present in a mixture such as dried milk. The material would then become sticky and lumpy,
making it undesirable. Salwin [2015] observed that the equilibrium condition obtained is not an
equal moisture content in all components in multicomponent mixture, but an equal activity
Many food components may be present in several states: crystalline solids, amorphous solids
either rubbery or glassy , aqueous solution, or bound to other components. Sorption in such
systems is complex. Crystalline sugars adsorb very little water, but amorphous sugars adsorb
substantially more water at the same conditions. The adsorption of water results in breaking of
some hydrogen bond and an increase in mobility of sugar molecules, resulting eventually in the
sugars transforming to the crystalline state. In this process the sugar loses water Karel [2017].
However, the sugar–polymer interaction and physical state play an important role in separating
out water from the system. Gelatinization followed by freeze drying results in only minor
differences in water-binding behavior of water activity up to 0.94; above 0.95 the gelatinized
samples adsorb considerably more water. Saltmarch and Labuza [2017] studied the effects of
water activity and temperature on the transition of lactose from the amorphous to the crystalline
state. Results from scanning electron microscopy indicated that lactose crystallized at 0.40, 0.33,
and 0.33 water activity after 1 week at 25°C, 35°C, and 45°C, respectively. Water activity also
influences protein conformation. The annealing effect of water, time, and temperature can alter
the structural and functional properties of cereal starch (Figures 20.5 and 20.6). When crystalline
starch is transformed to amorphous form, polar sites develop in the starch molecule, which could
form hydrogen bonds with water molecules Munzing [2017].
Schematic model of starch structure during amorphous and crystalline states. (From
Munzing, K. 2020. Thermochim. Acta 193: 441–448.)
Annealing effects of starch induced by water, temperature, and time. (From Munzing, K.
2015. Thermochim. Acta 193: 441–448.)
B. Temperature
Above Freezing
Below Freezing
Information in the literature on water activity of the frozen state below freezing is limited
Kapsalis [2018]. The vapor pressures of animal tissues over the temperature span of 26°C to 1°C
ranged from 13% to 20% lower than those of pure ice at the same temperature Hill and
Sunderland [2016]. Other researchers demonstrated that the vapor pressures of frozen biological
materials were equal to the vapor pressure of ice at the same temperatures Karel [2017]. Water
activity values at subfreezing temperatures can be calculated (rather than measured) as [70]
The equation indicates that water activity does not depend on the composition, but only on the
temperature. In a two-phase system (ice and solution) at equilibrium, the vapor pressure of solid
water as ice crystals and the interstitial concentrated solution are identical; thus, water activity
depends only on the temperature, and not on the nature and initial concentration of solutes,
present in the third or fourth phase (i.e., irrespective of the kind of food). This creates a basis to
estimate the water activity of foods below freezing using Equation 20.4. Thus, Fennema [2016]
concluded that changes in properties could occur below freezing without any change in water
activity. These include changes in diffusion properties, addition of additives or preservatives, and
disruption of cellular systems. The water activity data of ice from 0°C to 50°C are correlated
with an exponential function as
( )
a w =8.727 [ exp 595.1 ¿
T
where T is in K. The maximum error in prediction is 0.012 unit water activity and the average is
0.0066, respectively. The data of Fennema [2016] were used to develop the above correlation.
Water activity (aw) plays a crucial role in microbial growth in foods. Microorganisms such as
bacteria, yeasts, and molds require a certain level of water activity to thrive. The water activity of
a food product is defined as the ratio between the vapor pressure of the food itself and the vapor
pressure of distilled water under the same conditions. This value indicates the amount of
moisture available in the product for microbial activity.
Most foods have a water activity above 0.95, providing sufficient moisture for microbial growth.
By controlling the water activity to 0.85 or less in the finished product, it can inhibit the growth
of bacteria, yeasts, and molds. Lowering water activity limits the availability of free water that
microorganisms need for growth, thus acting as a preservation method.
Microorganisms have specific water activity requirements for growth; bacteria typically require
water activity values of at least 0.91, while fungi need at least 0.6 to support their growth. Every
microorganism has a threshold below which it will not grow due to insufficient water activity.
(Hill, 2003)
To manipulate water activity in food products, ingredients like sodium chloride, sucrose, alcohol,
propylene glycol, or glycerin can be added or adjusted to reduce water activity levels. This
process can make the preparation self-preserving by limiting microbial growth opportunities.
Enzymatic Activity
Enzyme-catalyzed reactions can proceed in foods with relatively low water contents. Karel
[2017] summarized two features of the results mentioned in the literature as follows: (i) The rate
of hydrolysis increases with increasing water activity, with the reaction being extremely slow at
very low activities. (ii) At each water activity, there appears to be a maximum extent of
hydrolysis, which also increases with water content. The apparent cessation of the reaction at low
moisture cannot be because of irreversible inactivation of the enzyme, but because upon
humidification to a higher water activity, hydrolysis is resumed at a rate characteristic of the
newly obtained water activity . Karel [2017]. Silver [2018] investigated a model system
consisting of avicel, sucrose, and invertase and found that the reaction velocity increased with
water activity. Complete conversion of the substrate was observed for water activities greater
than or equal to 0.75. Below water activities of 0.75, the reaction continued to 100% hydrolysis.
In solid media, water activity can affect reactions in two ways: lack of reactant mobility and
alteration of active conformation of substrate and enzymatic protein Tome et al [2017]. Effects of
varying the enzyme-to-substrate ratios on reaction velocity and the effect of water activity on the
activation energy for the reaction could not be explained by a simple diffusion model, but
required more complex postulates Karel [2017]: (i) The diffusion resistance is localized in a shell
adjacent to the enzymes. (ii) At low water activities, the reduced hydration produces
conformational changes in the enzyme affecting its catalytic activity. Tome et al. [2017] tested
the simple diffusion-related hypothesis on the basis of experiments in liquid systems in which
water activity was reduced by the addition of glycerol, ethylene glycol, propylene glycol,
diethylene glycol, sorbitol, methanol, or ethanol. In these solutions, the effects of
polyphenoloxidase on tyrosine were very similar to those obtained in solid systems. The
optimum pH of activity is shifted slightly toward alkaline values. Three characteristic curves
were observed: (i) for low water activity, there was almost a total inhibition, (ii) in the
intermediate range, reaction rate was very dependent on water activity, and (iii) for high water
activity zones, activity was weakly affected by organic
Source: Drapron, R. 2019. In: Properties of Water in Foods. (Simato, D. and Multon, J. L.,
eds.) Martinus Nijhoff Publishers, Dordrech
additives. In general, the rate increased rapidly with increasing water activity, and the reaction
stopped at a certain level before all reactants were consumed; the higher the water content, the
higher the plateau. The authors were unable to find a correlation of enzyme activity with
viscosity, solubility of oxygen and tyrosine, or dielectric constant. It also appeared that the more
the mixture deviated from ideality, the more the enzymatic activity was inhibited, regardless of
whether the deviation was positive or negative. Thus, solvent–water interaction is the main
parameter in polyphenoloxidase inhibition. The minimum water activities for enzymatic
reactions in selected food systems are given in the above Table
To address these challenges, novel techniques have been developed to control enzymatic
reactions in foods more effectively. Some of these techniques include:
2. Use of “Killer Enzymes”: Certain enzymes known as “killer enzymes” can be used to
target and inhibit specific enzymatic activities that lead to food spoilage.
3. Ionizing Radiation: Ionizing radiation has been explored as a method to control enzyme
activity in foods by disrupting enzyme structures.
Lipid Oxidation
Lipid oxidation is one of the leading causes of food spoilage. It refers to how unsaturated fatty
acids in fats are slowly oxidized when exposed to oxygen in air, light, and metal ion. It includes
auto-oxidation, photooxidation, and enzymatic oxidation Barden (2016). Auto-oxidation is a
free-radical chain reaction, the primary interaction between unsaturated fatty acids and oxygen
Wang (2023). In the initiation period, oil molecules produce free radicals under the effect of
light, heat, or metal catalysts. The propagation period and termination period of the free-radical
chain reaction are followed. The products of free radical and non-free radical reaction
compounds are still free radicals. Only the non-free radical compounds are formed when free
radicals react with free radicals, and the chain reaction is terminated (Figures 2D–F). Rancidity is
triggered when lipid auto-oxidation accumulates to a certain degree Wang (2016). It could also
produce aroma substances formed by large amounts of carbonyls, which contribute to the
formation of meat characteristics and flavor Zhou (2022).
Hydroperoxides are the main products of lipid auto-oxidation, and the oxidation of different fatty
acids could produce several hydroperoxides Ahmad (2023). The hydroperoxide was formed by
free radicals, including the removal of a hydrogen atom from the α-methylene group of the
double bond in the lipid. In this process, allyl radicals would be further formed. The electrons on
allyl radicals could be delocalized at three carbon atoms, as in oleic acid, or delocalized at five
carbon atoms, as in linoleic acid.
C. Non-Enzymatic Browning Reactions
Browning reactions in foods affect nutritional value as well as color and texture Kopelman
[2017]. The induction period, defined as the time to visually detectable browning, is inversely
proportional to water activity Kopelman [2018]. Browning reactions are influenced by the types
of reactant sugars and amines, pH, temperature, water activity, and the types of solutes or
humectants used to adjust the water activity Troller [2017].
Browning
There are three major pathways by which nonenzymatic browning can occur: high-temperature
caramelization, ascorbic acid oxidation, and the Maillard reaction Kopelman [2017]. The
browning reaction of sugars heated above their melting point in the absence of proteins or amino
acids is called caramelization. This can be either beneficial or detrimental to the quality of a food
product and can be prevented by avoiding high-temperature processing and low storage
temperatures. It is enhanced in alkaline or acid conditions and is used to make commercial
caramel colorings and flavors. Ascorbic acid (vitamin C) oxidation, a second type of browning
reaction, is catalyzed by low pH and elevated temperatures. The decomposition products
resulting from the oxidation of ascorbic acid cause a brown discoloration as well as decreased
nutritional value. The Maillard reaction is a result of reducing compounds, primarily sugars,
reacting with proteins or free amine groups. This changes both the chemical and the
physiological properties of the protein. In general, the accumulation of brown pigments is the
most obvious indication that Maillard browning has occurred in a food containing both
carbohydrate and protein. It is used as an indicator of excessive thermal processing in the milk
industry Kopelman [2017]. In the early stages of the Maillard reaction, the carbonyl group of the
reducing sugar reacts with the free amino group of the amino acid to form a Schiff base and then
the N-substituted glycosylamine as well as a molecule of water. Glycosylamines are converted to
1-amino-1-deoxy-2-ketose by Amadori rearrangement (cyclization and isomerization) Lomauro
[2018]. The Maillard reactions forming Amadori compounds do not cause browning but do
reduce the nutritive value. The advanced Maillard reaction has five pathways. The first pathways
start from the 1,2-enol or 2,3-enol forms of the Amadori product, yielding various flavor
compounds. The third pathway is Strecker degradation, which involves oxidative degradation of
amino acids by the dicarbonyls produced in the first two pathways. The fourth pathway involves
transamination of the Schiff base. The fifth pathway starts with a second substitution of the
amino-deoxyketose. The final step of the advanced Maillard reaction is the formation of many
heterocyclic compounds, such as pyrazines and pyroles Lomauro [2018]. Brown melanoidin
pigments are produced in the final stage of the Maillard reaction. The pigments are formed by
polymerization of the reactive compounds produced during the advanced Maillard reaction, such
as unsaturated carbonyl compounds and furfural. The polymers have a molecular weight greater
than 1000 and are relatively inert. These pathways depend upon environmental conditions such
as temperature and pH.
Texture
Rockland [2017] defined food texture as a function of localized moisture sorption isotherms as
follows: (i) region I (low water activity)—dry, hard, crisp, and shrunken, (ii) region II
(intermediate water activity)—dry, firm, and flexible, (iii) region III (high water activity)—
moist, juicy, soft, flaccid, swollen, stickiness. The effect of water activity on textural
measurements for different types of foods is reviewed by Bourne [2016]. Presently, there are
insufficient data to predict what the textural properties of a given type of food will be at a given
water activity, and no sound theories exist to predict in advance the textural properties of a food
at a given water activity. Cenkowski et al. [2022] studied the mechanical behavior of canola
kernels by bringing them to equilibrium, adsorption or desorption, at the same final moisture.
The ratio of elasticity was 18%–38% higher for kernels brought to equilibrium through
adsorption than those through desorption for a moisture range of 9.5%–7.5% (dry basis). At
higher moisture contents, the differences in modules of elasticity were not significant. In case of
dry snacks, the loss of crispness occurred close to BET monolayer Labuza [2015]. In case of
potato chips [108] and corn chips [2020], the critical water activity when the product was
unacceptable was found to be 0.40 water activity. The change in sensory crispness of potato
chips, popcorn, puffed corn curls, and saltines generally fell in the 0.35–0.50 water activity range
Katz [2017]. Instron analysis showed that the force–deformation curve changed distinctly near
critical aw for saltines and puffed corn curls, while the curve changed more gradually with
increasing aw for popcorn.
The growing recognition of the water activity principle is illustrated by its incorporation into
U.S. Food and Drug Administration (FDA) and U.S. Department of Agriculture (USDA)
regulations, Good Manufacturing Practices (GMP) and Hazard Analysis & Critical Control
Points (HACCP) requirements, and most recently in NSF International Draft Standard 75. The
purpose of these regulations is to detail the specific requirements, critical control points and
practices to be followed by industry to assure that products are produced under sanitary
conditions and are pure, wholesome and safe. New instrument technologies have vastly
improved speed, accuracy and reliability of water activity measurements and are definitely a
needed tool for food safety and quality.
Throughout history man has controlled the water activity of food through drying, addition of salt
or sugar and freezing such that the food becomes stable to microbial and chemical deterioration.
Food manufacturers today have the same goal of making a stable and safe product. This means
that the products must be wholesome and not endanger the health of the consumer with
microorganisms or their toxins. The advantage today is in the knowledge and understanding of
the importance of water activity in controlling microbial growth and thus upon the shelf life and
safety of a product.
The Centers for Disease Control (CDC) stated foodborne disease is responsible for
approximately 76 million illnesses, 325,000 hospitalizations and 5,000 deaths annually in the
United States. Known pathogens, such as Salmonella, Escherichia
coli O157:H7, Campylobacter and Listeria monocytogenes, account for an estimated 14 million
illnesses, 60,000 hospitalizations and 1,800 deaths alone. With staggering statistics like these one
would not believe that the U.S. has the safest food supply. Based on Food Net surveillance data
from 1997 to 1999, illness from the most common bacterial foodborne pathogens declined nearly
20%. This decline represents at least 855,000 fewer Americans each year suffering from
foodborne illness caused by bacteria since 1997. By using water activity and controlling major
food risks, such as microbial contaminants, the food industry can better ensure the safety of its
products.
The consequence of a microbiological failure, particularly as they relate to product recalls, can
be very costly. Brand recognition and sales may ultimately suffer as a result of consumers
relating the recall to other products manufactured by a particular company. In a world of
increasing pressures and diminishing resources, the need to strengthen microbiological quality
assurance programs has not abated. In fact, there is more pressure than ever on the management
of microbiological quality. Food safety must be controlled during the production process from
beginning to end, rather than relying on detection of problems in the finished product.
Conclusion
Foods' processes, sensory qualities, shelf life, and physical attributes are all greatly influenced by
their water activity. The ratio of a system's water vapor pressure to that of pure water at the same
temperature, or the equilibrium relative humidity of the air surrounding the system at the same
temperature, is what is meant to be understood as this thermodynamic attribute. There are
numerous ways to reduce or regulate water activity, including adding solutes and removing from
the water. Water can be eliminated using a variety of processes, including baking, extrusion,
centrifugation, concentration, drying, and frying. Foods can have solutes added to them to
enhance their functional and sensory qualities while lowering their water activity.
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