Water Activity and Safety of Bakery Products

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WATER ACTIVITY:

FOOD SAFETY

Research Department

- TECHNICAL BULLETIN
Editor - Gur Ranhotra I Volume XII, Issue 6 I June, 1990

WATER ACTIVITY AND SAFETY


OF BAKERY PRODUCTS
Wulf Doerry
Director, Cereal Technology Research
American Institute of Baking

INTRODUCTION
The term water activity (abbreviated as a,) was vir- TABLE I
tually unknown in the baking industry until about ten
WATER ACTIVITY AND SHELF LIFE
years ago. That has changed. The measurement and
concept of a, is now gaining wide acceptance for con-
1. Moisture Migration (Gain or Loss).
trolling and monitoring the safety of baked products.
2. Microbial Activity.
The term a, was introduced in 1953 by W.F. Scott
3. Chemical Reactions.
when he reported on the moisture requirements of the
4. Physico-chemical Changes.
bacterium Staphylococcus aureus. A, is a measure of
the free moisture in a product and is defined as the ratio
of the partial pressure of water in the food to the vapor
pressure of pure water at the same temperature. By def- moisture in the crumb, and it will be tough and very
inition, the a, of pure water equals one. This bulletin chewy, instead of crispy.
discusses, with appropriate examples, the usefulness of Another example is a jelly-filled single-serving type
the a, concept in insuring the safety of bakery foods; an snack cake. The jelly, unless carefully formulated, has a
earlier bulletin (1) discussed the basics of a, concept. higher a, than the cake itself. As such, the filling will
soak into the crumb. This is especially annoying where a
MEASURING WATER ACTIVITY small white or yellow variety snack cake contains a red
A, is measured, with a hygrometer or by electronic jelly filling.
instruments, as the percent relative humidity of the at- A third example is a doughnut enrobed with a choco-
mosphere surrounding the food product when it is in late flavored compound coating. If one wonders why
equilibrium with the vapor pressure of water in the food. chocolate doughnuts tend to be dry within 24 hours, it is
This vapor pressure is related to the food’s tendency to because of the a, of the doughnut itself. When starting
lose moisture. A, is expressed as the decimal of the out with a nice and moist doughnut and packaging it in
equilibrium relative humidity (ERH). In other words, a sealed bag or box, it is often found that the coating will
a,+,= % ERH+lOO. melt. Unfortunately, many bakers do not understand
that this is the result of moisture migration and believe
WATER ACTIVITY AND SHELF LIFE that the fat in the coating is melting. Consequently, they
By controlling the a, of bakery foods and their com- ask the coating manufacturer to raise the melting point
ponents, the shelf-life of the product can be effectively of the fat to a level where it becomes waxy, but without
controlled with primary consideration given to the four the desired result.
factors listed in Table I.
Microbial Activity
Moisture Migration Another reason for controlling the a,,, of foods is to
If one combines two components with different a,, control microbial activity. Microbes are the major cause
moisture migration will occur from the component with of food spoilage. At a, above 0.91, bacteria thrive and
the higher a, to the portion of the food that has a lower cause the food to decay (Table II). Bacteria are not as
a,. For example, when a crusty loaf of French bread is much of a problem in baked products as they are in
baked, the a, of the crust will be much lower than that other foods, because the baking process tends to kill off
of the crumb. If this loaf is packaged to prevent moisture the bacteria and allows only some spores to survive.
loss, the crust will reach an equilibrium with the Yeasts, particularly wild yeasts, are a major problem
formulated. By lowering the a, by means other than by
TABLE II evaporating moisture, one is actually able to retain
moisture in the food without running the risk of in-
MICROBIAL ACTIVITY AND OTHER
creased microbial activity.
CAUSES OF FOOD SPOILAGE
Physio-chemical Changes
Major Cause 4, Range Even though the packaging prevents moisture loss to
Bacteria 0.91-1.00 the environment, semi-moist bakery foods stale and be-
Yeasts 0.87-0.91 come dry to the touch and in mouthfeel. The a, of the
Molds 0.80-0.87 product is not affected by the staling process; the mois-
Halophilic Bacteria 0.75-0.80 ture is simply made unavailable to our sensory percep-
Xerophilic Molds 0.65-0.75 tion by crystallization (retrogradation) of starch.
Osmophilic Yeasts 0.60-0.65 Products which are baked to a very low moisture level
Maillard Reactions 0.60-0.80 (cookies and crackers, for example) have a very low a,.
Enzymes (Amylases, etc.) 0.95-1.00 Starch retrogradation in these products proceeds at a
Lipase 0.1 much slower rate and may even cease. Therefore, these
Oxidation of Fats 0.01-0.50 products have a long shelf life (the shelf-life of a product
is inversely related to the content of moisture in it). In
contrast, products such as bread and rolls which can be
formulated to retain more moisture than will be physi-
at a, as low as 0.87. They are the major cause of fer- cally bound by starch retrogradation, will not be per-
mentation. Their presence is frequently noticed as a ceived as dry. This approach, however, increases the a,
fruity aroma. Pie fillings are often spoiled by wild yeasts and, thus, stimulates microbial activity.
and these organisms can also be found in corn syrups.
Controlled or modified atmospheric packaging does not MICROBIAL ACTIVITY AND FOOD SPOILAGE
prevent yeast spores from germinating. All microbial causes of food spoilage compete with
Generally, when the baker speaks of microbial spoil- each other and may act upon the product simultaneous-
age, he or she usually means spoilage due to mold. ly. On the other hand, as one organism is favored by the
Mold spores are abundant in any bakery atmosphere; prevailing conditions, it can suppress the other organ-
one gram of flour contains on the average 9000 mold isms. For instance, when oxygen is removed from the
spores. An estimated 7000 to 8000 mold spores may package, it may inhibit mold growth; but at the same
settle every hour on an area of one square meter. time it may favor the propagation of the Clostridium
Therefore, it is important to segregate the baked prod- botulinum bacterium, which can produce a very power-
uct from the general production area. Flour dust moved ful, but heat sensitive, toxin.
by natural air currents or fans is the major contaminant Another example is the balance of yeast fermentation
of bakery products during the cooling process and be- and the acid production by lactic acid bacteria. At tem-
fore packaging. Unlike some bacterial spores, mold peratures between 80 and 9O0F and under anaerobic
spores do not survive the baking process and all mold conditions, the fermentation of sugars by the baker’s
growth originates from post-bake contaminations. yeast is favored. The production of lactic acid by bac-
teria is suppressed. However, cooling the dough after
Chemkal Reactions make-up to a temperature where yeast fermentation is
Chemical reactions are very dependent on the retarded will give the lactic acid bacteria a chance to
amount of free water available in foods. Maillard or produce a variety of organic acids that can react with the
browning reactions are most favored by a, around alcohol from the yeast fermentation to form desirable
0.75, while oxidative rancidity proceeds at the fastest flavor components. This is the reason why the warmer
rate at a, lower than 0.3. no-time doughs will not produce good tasting bread,
The Maillard reaction - a reaction between amino rolls, or bagels, unless one adds high levels of nonfat
acids in proteins and simple reducing sugars - is very dry milk or other taste producing ingredients. However,
important for the baker, since it produces the color and many bagel bakers use the dough retarding process to
the slightly bitter taste in the crust of bakery foods. To enhance the flavor of their product.
enhance this reaction, malt is added to many crusty It is apparent that as conditions are changed to inhibit
breads and rolls. Malt sugar provides the desired taste one microbial organism or one chemical reaction, be it
after it has reacted with proteins in the crust, where by altering the a,, by removal of oxygen from the at-
evaporation of moisture has reduced the a, to the level mosphere, or by decreasing or increasing the tempera-
at which browning takes place. ture, one is faced with entirely different causes for food
When invert sugar, honey, or high fructose corn syrup spoilage. The frightening aspect of this is that some
are added to cookie doughs, the a, in the finished types of spoilage may not be obvious to the consumer
cookie is reduced and more moisture is retained in the and, therefore, may have severe consequences.
product. This is how soft and dual-textured cookies are

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Spoilage Associated With Bacteria totally spoiled. Although it is seldom found today in
Although bakery foods are seldom spoiled by bac- foods manufactured in large bakeries, it has become
teria, bacterial spoilage can still occur, and often the on- quite a problem for bakers who like to abstain from
ly way that these organisms manifest themselves is chemical inhibitors. Lately, rope was seen in compact
through food poisoning. This occurs when an unsus- whole grain bread, as well as in bran muffins and in
pecting consumer ingests toxins with food. One of the quick breads.
most studied bacteria in this regard is Staphylococcus The other troublesome microbe is the Bacillus prodi-
aureus. This bacterium can propagate at a a, as low as giosus variant Serratia marcesceus. It causes red spots
0.86. Fortunately, toxin production does not occur at a in bread and the symptoms are known in the industry as
aW less than 0.94. Although the bacteria are generally “bleeding bread.” Fo~unately, there have not been
killed during the baking process, the toxins usually sur- many reports in recent years that indicate that this
vive. Therefore, it is extremely important to protect soft bacillus is a real problem.
pie fillings, such as custards and summer custards, from
being infected with Staphylococcus aureus bacteria. Spoilage Associated With Yeast
Another common cause of food poisoning is Salmon- As with bacteria, it is difficult to see the presence of
ella bacteria. Although they require a relatively high a, wild yeasts (Table III) until the damage is done. Al-
for propagation, their tolerance to heat increases in the though bakers’ yeast, a strain of Saccharomyces cere-
presence of higher levels of sucrose. Even though it is visiae, can be active at s as low as 0.9, anaerobic fer-
specified that ingredients must be free of any salmonel- mentation by this organism slows rapidly at a, less than
lae, there is very little information published about how 0.97. The same is true for most other wild yeasts, such
a, affects these bacilli. as Candida utilis. However, there is a group of osmo-
Clostridium botulinum is feared by everyone in the philic yeasts (tolerate high osmotic pressures) that thrive
food industry. It is an anaerobic organism that thrives
best in the absence of oxygen. Its very potent toxins are
produced at a, above 0.94. But unlike the toxins pro-
TABLE III
duced by Staphylococci, the botulinum toxins can easily
be destroyed by heat. The U.S. Army used to solve the WILD YEAST AND WATER ACTIVITY
botulinurn problem by simply requiring a moisture con-
tent of less than 35% in canned bread and a maximum For Growth
crumb pH of 4.8. This, presumably, lowers the a, of
% Temperature
bread to a level where this organism is no longer a threat
Yeast (Minimum) (OC)
to health.
Two other bacteria, relatively unknown to the con- Saccharomyces
sumer, are also feared by the baker. One is the Bacillus cerevisiae 0.90 27
mesentericus variant of Bacillus subtilis. This organism is Saccharomyces
the cause of rope formation in bakery products with a rouxii 0.62 30
a, of 0.9 or higher. The vegetative form of the bacillus is Candida utilis 0.94 20
sensitive to heat, but the spores can survive the baking
process and, within a few days, the product can be

TABLE IV
WATEB ACTIVITY FOR MOLD GROWTH

For Growth

% Temperature
Mold (Minimum) (OC)
Rhizopus 0.93 ?
Mucor spinosus 0.93 25
Penicillium cyclopium 0.82
Penicillium patulum 0.82 ;:
Aspergillus flavus 0.78 43
Aspergillus ochraceus 0.77 25
Aspergillus niger 0.78 43
Aspergillus echinulatus 0.62 25
Monascus biiporus 0.61 25

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TABLE V
MOISTURE CONTENT AND WATER ACTIVITIES OF COMMON INGREDIENTS

Ingredient Moisture (X) 4,


Fruit 88-95 0.98-0.99
Grain 13 0.70
Dry Milk 3 0.70
Dried Whole Eggs 10-11 0.70
Flour 14 0.68-0.70
Sugar (Sucrose) 3 0.60-0.70
Corn Syrup (43 DE) 19.7 0.69-0.70
High Fructose Corn Syrup (42%) 29 0.76
Invert Sugar 23 0.75
Raisins 17 0.60

at a, as low as 0.62. One variety of these osmophilic


yeasts is Saccharomyces rouxii. TABLE VI
Evidence of these osmophilic yeasts has been found
in fruit topped Danish pastries packaged in a controlled TYPICAL WATER ACTIVITIES
atmosphere. Also, any manufacturer of long shelf-life OF BAKERY PRODUCTS
bakery products who experiences a build-up of pressure
within the package, also known as “ballooning”, may Product &,
have become a victim of osmophilic yeasts. A fruity or 1.00
Water
solvent-like odor that dissipates very rapidly is generally Breads, Yeast-Raised Doughnuts 0.96-0.98
an indicator of the presence of wild yeasts. Fruit Pie Fillings 0.95-0.98
Spoilage Associated With Mold Cheeses 0.91-0.95
Cakes, Cake Doughnuts 0.85-0.87
When the baker discusses microbial spoilage, bacteria
Chocolate Coated Doughnuts 0.82-0.83
or yeasts are seldom considered; most often the baker
Creme Filled Snack Cakes 0.78-0.81
refers to the growth of mold colonies on bakery prod-
Soft Cookies 0.50-0.78
ucts (Table IV). Mold is visible to the consumer and to
Cookies, Crackers 0.20-0.30
the baker and this can be very upsetting.
Whereas the spores of some bacilli (probably also of
some wild yeasts) are able to survive the baking process,
mold spores are not able to survive. All infestation with Although xerophilic (dry-loving) molds are not that
mold spores, therefore, occurs after the product has common in bakeries, Aspergillus echinulatus and
been baked. Many bakery ingredients are loaded with Monascus bisporus can still be a threat at the very low
mold spores. Flour, cocoa, spices, unpeeled fruit and a, range of 0.61 and slightly higher.
especially air are carriers of these spores. Other sources
are garbage, catch pans for condensates, washing areas, SUSCEPTIBILITY OF INGREDIENTS
floor drains, equipment, and production personnel. AND PRODUCTS TO MICROBIAL SPOILAGE
There are four types of mold commonly found on When one looks at the a, of many common ingredi-
bread products. The black Mucor and Rhizopus molds ents, one can recognize their susceptibility to microbial
require a minimal a, of 0.93, which includes most yeast spoilage (Table V) . Fruit is prone to spoilage by all three
raised products. However, these two types of mold major groups of microbes - bacteria, yeast and mold.
have not been reported to produce toxins. Grain and dry ingredients can be attacked by xerophilic
The penicillia molds grow at a,,, above 0.8. Although molds. Syrups are prone to fermentation by osmophilic
most penicillia do not produce toxins at a, below 0.95, yeasts and they also support the growth of some molds.
researchers have found ochratoxin and pat&n in Peni- However, only the fruit is an appropriate medium for
cillium cyclopium and Penicillium pat&m cultures toxin production.
grown at a,,, as low as 0.87 and 0.85, respectively. Bakery foods are much more endangered by micro-
Aspergilli grow at a, above 0.76. Aflatoxin produc- bial activity than bakery ingredients (Table VI). Yeast
tion by Aspergillus flavus has been reported at a, of raised products support mold on the exterior and allow
0.83 and penicillic acid by Aspergillus ochraceus at the spores of some bacilli and wild yeasts to germinate inter-
even lower a, of 0.80. nally. Fruit pie fillings and cheeses will not only do the

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same, but the soft pie fillings, like custards and summer will more likely occur in low moisture foods, like
custards, will also provide an optimum environment for cookies, than in relatively high moisture foods, like
such pathogens as Salmonellae and Staphylococci. cakes and muffin batters.
Chemically leavened bakery foods, such as cakes, A, is governed not by weight, but by the number of
snack cakes, and cake doughnuts are primarily threat- molecules dissolved in the food’s moisture (Raoult’s
ened by molds, just like the very moist soft cookies. law). Only the dissolved molecules affect the partial
However, most cookies, and certainly crackers, are pressure of the water vapor or the ERH. For a given
quite safe from microbial spoilage. weight of sugars or salts dissolved in water, there are
‘more molecules dissolved when their molecular weights
FACTORS AFFECTING WATER ACTIVITY are small or when they are ionized, like regular table
IN BAKED GOODS salt. A given amount of dissolved sugar solids will con-
A variety of factors affect the a, in foods (Table VII). tain just a little more than half as many molecules when
Regarding ingredients, only those that dissolve in water one uses regular sugar, or sucrose, rather than dextrose
or form bonds with water molecules affect the a,,, in or fructose.
foods. Sugars, alcohols, and various soluble salts be- The temperature of the food also affects its a,. As is
long to the first group. Proteins with undenatured polar well known, one can accelerate the drying process by
groups belong to the second category. However, their raising the temperature of the product. This is because
effect is relatively small and it decreases as the pH of the the water’s vapor pressure increases and, thus, its a,.
food approaches the isoelectric point of the protein, that As one freezes the food, its a, is lowered.
is when all the positive and negative charges on the pro- Fruit and other natural products become soft and wa-
tein molecule are balanced. tery when they decay. When one checks the a,, it is
As mentioned earlier, only dissolved molecules re- found that microbial activity which causes the break-
duce a,. Because starches and gums are not very solu- down of the cell structure actually raises the a,.
ble, they will not affect a, significantly, although they Whereas the original a, of the food may not have been
are excellent as thickeners, and increase the viscosity of sufficient to support the production of toxins, the lique-
batters and doughs. Reducing sugars and polyalcohols faction of the organic matter by microbes frequently
are another matter. These are very reactive ingredients raises it to this level, so that severe food poisoning may
and may not survive the baking process in their original result.
form. For example, in one case, a good portion of 5% When batters and doughs are baked, there is not only
glycerine added to bread doughs was reported to have the formation of a crust and crumb structure, but the
reacted during the baking process and was no longer food is also partially or completely dried. As more and
able to function as a humectant. more water is lost, the a, is lowered, too. Baking, thus,
Many bakers also experienced problems with using becomes a very important method for lowering the a, of
large amounts of corn sugar, or dextrose, during the long shelf-life foods to a level safe from microbial activity.
sugar shortage in 1974. The dextrose crystallized in the Besides offering protection from contact with unwant-
cakes and the product became dry and crumbly. When ed contaminants, the packaging is generally also de-
bakers tried in 1977 to replace cocoa with carob powder signed to control the a, of the food. High moisture bar-
that had been only lightly roasted, they again exper- rier films inhibit the loss or gain of moisture to and from
ienced the same problems as three years earlier with the environment. However, sometimes a differential in
corn sugar. However, when the reducing sugars in the moisture content between the exterior and interior of a
carob were caramelized during the manufacture of high- bakery food is preferred and the loss of free water is al-
ly roasted powder, no ill effects in cakes were noted. It lowed at a controlled rate. Typical examples are crusty
is, thus, apparent that not all the reducing sugars added breads and rolls, fried pies and glazed yeast raised
to a batter or dough will retain their humectancy. This doughnuts. They are wrapped in perforated or low
moisture barrier films.
Although the application of edible moisture barriers to
food is not a new concept, the baking industry has gen-
TABLE VII erally not been very successful with this technology. The
FACTORS AFFECTING WATER ACTIVITY industry, however, does use nut meats, raisins, and
IN BAKED GOODS other ingredients coated with oil or other fat-like materi-
als. The pizza industry even inhibits moisture migration
1. Amount of ingredients dissolved in food moisture from the topping to the crust by brushing a stable
(Raoult’s Law). vegetable oil onto the crust. The baker, however, has
2. Molecular weight of dissolved ingredients. never been able to apply an effective barrier to yeast
3. Temperature. raised doughnuts or fried pies to stop the migration of
4. Microbial activity. moisture from the product to the sugar glaze.
5. Environment (baking, storage).
6. Moisture barriers (packaging, coatings).

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CONTROLLING WATER ACTIVITY free water and this, in turn, can shift the conditions in
TO ADVANTAGE such a way that other microbes are favored.
Even though good progress has been made in under-
standing and controlling the a, in foods, one soon SUMMARY
reaches the limits of available technologies. As sweeten- As the baking industry searches for new technologies
ers, salts and fats are removed and as fibrous ingredi- to fill the need for specially formulated foods and to ex-
ents and more water are added to meet nutritional tend their shelf-life, a, is no longer a mere concept. It has
guidelines and textural expectations by the consumer, become a familiar term and an important tool for achiev-
one soon finds that the final products are subject to in- ing the goal of providing the American public with food
creased microbial activity. The question now arises: how that is more nutritious and safer than ever before.
can one reduce this activity to relatively safe levels? For-
tunately, all our weapons in this fight have an accumula-
REFERENCE
tive effect on microbes. 1. DAVIS, A. Water Activity (a;) - New Interest in an
In discussing the minimal a,,, for bacteria, yeasts, and Old Concept. Technical Bulletin, American Institute
molds to grow and propagate, one assumes that all of Baking, I1 (3): 1980.
other conditions (temperature, acidity, solute type, in-
hibitors, competing microbes) were very favorable for
these organisms. As one makes these conditions less fa-
vorable, the minimum a, for a microbe’s growth in-
creases. For example, one can slow down food spoilage
significantly by refrigerating the food, and practically all
households in our country utilize this relatively simple
means to store food safely.
About 20 years ago, research showed that no patho-
genic organism produces toxins in a high acid food.
Gradually, federal, state, and local governments accept-
ed this finding and now their agencies allow bakers and
other food vendors to sell their wares from room tem-
perature shelves regardless of the product’s a,, as long
as the pH of this food is 4.5 or less.
Microbes sometimes do not respond in the same
manner to the various solutes used to reduce the a, in
the food. Some tolerate more sugar, others more salt or
polyalcohols.
Normally, different inhibitors are used to control dif-
ferent types of microbes. Propionates are effective
against Bacillus mesentericus and mold, but they will al-
low yeast fermentation at normal use levels. Sorbic acid
and its potassium salt are effective against molds and
wild yeasts; but the literature is not totally clear about
their effect on various bacteria. Benzoates are very pow-
erful inhibitors for all microbes. But, unfortunately, only
the undissociated acids are functional and, therefore,
the ability of the inhibitors to retard microbial activity
depends on the pH of the food medium. Benzoates lose
their effectiveness rapidly as the pH of the food in-
creases to above 4.5. Propionates are very suitable for
yeast raised products, since their optimum pH range is
up to 5.5. The effective pH range for sorbic acid and
sorbates is slightly higher.
Since any set of conditions favors particular microbes,
these will tend to suppress other organisms. Also, under
one condition an organism may propagate while under
a different condition it may ferment or produce toxins.
Yeast, for instance, will multiply in an atmosphere rich
with oxygen; but under anaerobic conditions, like in
sponges and doughs, yeast will ferment. As mentioned
earlier, microbial action can change the availability of

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