1.
5 Water activity
Deterioration of foods by micro-organisms can take place rapidly, whereas enzymic and
chemical reactions take place more slowly during storage. In either case the water content
is a very important factor controlling the rate of deterioration. The moisture content of
foods can be expressed either on a wet-weight basis:
mass of Wa
M
mass of sample
x 100 .28
mass of water
m
mass of water + solids
x 100 L.290
or on a dry-weight basis
mass of water
m
mass of solids L30
Lewis, 1990).
The dry-weight basis is more commonly used for processing calculations, whereas the
wet-weight basis is frequently quoted in food composition tables. It is important,
however, to note which system is used when expressing a result. Wet-weight basis is used
throughout this text unless otherwise stated.
A knowledge of the moisture content alone is not sufficient to predict the stability of
foods. Some foods are unstable at a low moisture content (for example peanut oil
deteriorates if the moisture content exceeds 0.6%), whereas other foods are stable at
relatively high moisture contents (for example potato starch is stable at 20% moisture)
(van den Berg. 1986). It is the availability of water for microbial, enzymic or chemical
activity that determines the shelf life of a food, and this is measured by the water activity
(aw) of a food, also known as the Relative Vapour Pressure (RVP).
Examples of unit operations that reduce the availability of water in foods include those
that physically remove water (dehydration (Chapter 15), evaporation (Chapter 13) and
freeze drying or freeze concentration (Chapter 22)) and those that immobilise water in the
food (for example by the use of humectants in 'intermediate-moisture' foods and by
formation of ice crystals in freezing (Chapter 21). Examples of the moisture content and
a of foods are shown in Table 1.12 and the effect of reduced a, on food stabilityis
shown in Table 1.13.
Water in food exerts a vapour pressure. The size of the vapour pressure depends
on:
the amount of water present
the temperature
the concentration of dissolved solutes (particularly salts and sugars) in the water.
Water activity is defined as 'the ratio of the vapour pressure of water in a food to the
saturated vapour pressure of water at the same temperature' (equation 1.31):
Properties of foods and processing theory 45
Table 1.12 Moisture content and water activity offoods
Moisture
content Water
Food (%) activity Degree of protection required
Ice (0°C) 100 1.00
Fresh meat 70 0.985
Bread 10 0.96 Package to prevent moisture loss
Ice (-10°C) 100 0.913
Marmalade 35 0.86
Ice (-20°C) 100 0.82
Wheat flour 14.5 0.712
Ice (-50°C) 100 0.62 Minimum protection or no packaging
Raisins 27 0.60 required
Macaroni 10 0.45
Cocoa powder 0.4
Boiled sweets 3.0 0.30
Biscuits 5.0 0.20 Package to prevent moisture uptake
Dried milk 3.5 0.11
Potato crisps 0.08
Vapour pressure of ice divided by vapour pressure of water.
Adapted from Troller and Christian (1978), van den Berg (1986) and Brenndorfer et al. (1985).
Table 1.13 The importance of water activity in
foods
aw Phenomenon Examples
1.00 Highly perishable freshfoods
0.95 Pseudomonas, Bacillus, Clostridium Foods with 40% sucrose or 7% salt,
perfringens and some yeasts inhibited cooked sausages, bread
Foods with 55% sucrose, 12% salt,
0.90 Lower limit for bacterial growth (general), cured ham, medium-age chesse.
Salmonella, Vibrio parahaemolyticus,
Clostridium botulinum, Lactobacillus, and some Intermediate-moisture foods
yeasts and fungi inhibited (a = 0.90 0.55)
0.85 Many yeasts inhibited Foods with 65% sucrose, 15% salt,
salami, mature cheese, margarine
0.80 Lower limit for most enzyme activity and Flour, rice (15-17% water) fruit cake
of most fungi: Straphlococcus sweetened condensed milk, fruit
growth aureus
inhibited syrups, fondant
0.75 Lower limit for halophilic bacteria Marzipan (15-17% water), jams
0.70 Lower limit for growth of most xerophilic fungi
0.65 Maximum velocity of Maillard reactions Rolled oats (10% water), fudge.
molasses, nuts
0.60 Lower limit for growth of osmophilic or Dried fruits (15-20% water), toffees,
xerophilic yeasts and fungi caramels (8% water), honey
0.55 Deoxyribonucleic acid becomes disordered
(lower limit for life to continue)
Dried foods (a = 0-0.55), spices,
0.50
noodles
0.40 Minimum oxidation velocity Whole egg powder (5% water)
0.30 Crackers, bread crusts (3-5% water)
0.25 Maximum heat resistance of bacterial spores
0.20 Whole milk powder (2-3% water),
dried vegetables (5% water).
cornflakes (5% water)
46 Food processing technology
aw
L.31
where P (Pa) = vapour pressure of the food, Po (Pa) = vapour pressure of pure water at
the same temperature. a is related to the moisture content number of
by a
equations,
including the following:
dw
C-1
M(1-a) MC MC .52
where aw =
water activity, M
moisture as percentage dry weight,
=
73/592 (dr
weight basis) of a monomolecular layer and C = a constant. A s.
on
described by Karel (1975).
A proportion of the total water in food is
a
strongly
bound to specific sites (for example
hydroxyl groups of polysaccharides,
carbonyl and amino groups of proteins, and hydrogen
bonding). When all sites are (statistically) occupied by adsorbed water the moisture content
is termed the BET
(Brunauer-Emmett-Teller) monolayer value (Fennema, 1996). Typical
examples include gelatin (11%), starch (11%), amorphous lactose (6%) and whole spray-
dried milk (3%). The BET
monolayer
which the food is most stable. At moisture
value therefore represents the moisture
content at
contents below this level, there is a
lipid oxidation and, at higher moisture contents, Maillard higher rate of
microbiological activities browning and then enzymic and
The movement of water
are
promoted (Fig. 1.15).
vapour from food to the surTOunding air
a
food (moisture content and depends upon both the
composition) and the condition of the air
(temperature and
humidity). At a constant temperature, the moisture content of food
equilibrium with water vapour in the surrounding air. The food then changes until it comes into
weight on storage under those conditions. This is called the neither gains nor loses
the food and the relative
humidity of the storage equilibrium moisture content of
relative humidity. When different values of atmosphere is known as the
equilibrium
content are plotted, a curve known as
relative humidity versus equilibrium moisture
a water
sorption isotherm is
Each food has a
unique set of sorption isotherms at different obtained (Fig. 1.16).
shape of the sorption isotherm is caused temperatures. The precise
by differences in the
physical structure, chemical
composition and extent of water binding within the
a
characteristic shape, similar to that shown in food, but all sorption isotherms have
point A, represents monolayer water, which is Fig. 1.16. The first part of the
curve, to
by drying. The second, very stable, unfreezable and not removed
adsorbed in multilayers within relatively straight part of the curve (AB)
the food and solutions of represents water
portion, (above point B) is "free' water condensed soluble components. The third
cells of a food. It is within the capillary structure
is easily removed mechanically
trapped within the food and held by
or in the
by only weak forces. It
Free water is availabledrying
and easily frozen, as
indicated by the
for
moisture content above microbial growth and enzyme steepness of the curve.
The sorption isotherm
point B on the curve is likely to activity,
be
and a food which has a
the effect of indicates the aw at which a food is susceptible to spoilage.
changes in moisture stable and allows
determine the rate and extent content on aw and hence on storage predictions of
of drying stability. It is used to
temperatures (Chapter 21) and the moisture(Chapter 15), the optimum frozen
materials (Chapter 24). barrier storage
properties required in
The rate of change in
packaging
ay on a
removed from a food sorption isotherm differs according to
whether moisture
1.16). This is termed a (desorption) or whether it is added to dry food is
hysteresis loop. The difference is (absorption) (Fig.
large in some foods (for example
Properties of foods and processing theory 47
1.0
Oxidation
0.5
.0
Browning
0.5
74/592
1.0
Enzyme activity
0.5
Mould growth
0.5
Bacterial growth ( - )
0.5 and toxin production (--J
0.4 0.6 O.8 1.0
Water activity
Fig. 1.15 Effect of water
activity on microbial, enzymic and chemical
(After Karel (1975).) changes to foods.
rice) and is
important for example in
determining the protection required against
uptake. moisture
1.5.1 Effect of aw on
foods
The effect of ay on
microbiological and selected biochemical reactions is shown in
and Table 1.13. Almost
inhibited below a
all microbial
activity is inhibited below aw 0.6, most Fig. 1.15
0.7, most yeasts are inhibited =
=
below a fungi are
0.8 and most bacteria
aw 0.9. The interaction =
below
chemical preservatives has anof aw with temperature, pH, oxygen and carbon
any one of the other important effect on the inhibition of microbial dioxide, or
environmental conditions is growth. When
the effect of reduced
ay is enhanced. This sub-optimal for a given micro-organism,
mechanisms which result in the permits the combination of several mild
value or sensory preservation of food without substantial loss of control
characteristics (Table 1.14)
(see also the 'Hurdle effect' in nutritional
Section 1.8.2).
48 Food processing technology
Desorption
25
20
15
O Adsorption
75/592
L
20 40 60 80 100
Relative humidity (%)
1.16 Water sorption isotherm.
Fig.
Table 1.14 Interaction of aw pH and temperature in selected foods
Food pH Shelf life Notes
Fresh meat >4.5 >0.95 days Preserve by chilling
0.95 weeks Ambient storage when packaged
Cooked meat >4.5
>4.5 <0.90 months Preserved by salt and low aw
Dry sausage
weeks Stable' while respiring
Fresh vegetables >4.5 >0.9
0.90 months Low pH maintained by packaging
Pickles <4.5
Bread >4.5 >0.95 days
Fruit cake >4.5 90 weeks Preserved by heat and low a
Milk >0.95 days Preserved by chilling
>4.5 weeks Preserved by low pH and chilling
Yoghurt <4.5 <0.95
Dried milk >4.5 <0.90 months Preserved by low aw
Enzymic activity virtually ceases at au values below the BET monolayer value. This is
due to the low substrate mobility and its inability to diffuse to the reactive site on the
enzyme. Chemical changes are more complex. The two most important that occur in
foods which have a low a, are Maillard browning and oxidation of lipids. The a that
causes the maximum rate of browning varies with different foods. However, in general, a
low a restricts the mobility of the reactants and browning is reduced. At a higher a
browning reaches a maximum. Water is a product of the condensation reactionin
browning and, at higher moisture levels, browning is slowed by 'end product inhibition
At high moisture contents, water dilutes the reactants and the rate of browning falls.
Oxidation of lipids occurs at low ay values owing to the action of free radicals. Above
the BET monolayer value, anti-oxidants and chelating agents (which sequester trace
metal catalysts) become soluble and reduce the rate of oxidation. At higher aw values the
catalytic activity of metals is reduced by hydration and the formation of insoluble
hydroxides but, at high aw values, metal catalysts become soluble, and the structure of the
food swells to expose more reactive sites (Fig. 1.15).
1.6 Effects of processing on the sensory characteristics of foods
There are a number of definitions of 'quality' of foods, which are discussed by Cardello
(1998). To the consumer, the most important quality atributes of a food are its sensory
