Calcium Propionate
Calcium Propionate
Calcium Propionate
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recommendation, guarantee, or warranty, either expressed or implied by the American Institute of Baking. Neither should the mention of registered brand names be construed as an endorsement of that
product by the American Institute of Baking. Material contained in this publication copyrighted, 2002, by the American Institute of Baking.
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TABLE I
replaced sugar, oil has replaced shortening, yeast tion (DOT) standards. In order to be considered non-
suspensions or cream yeast have replaced dry yeast, corrosive, it must be neutralized with a small amount
and liquid preservatives have replaced dry of calcium, sodium, or potassium ion to a pH of 4 to
preservatives. 6. With a pH in this range, the preservative maintains
When changes were made from dry to liquid its water solubility without precipitating and, thereby
preservatives, the physical form was altered, but the allows a low amount of water carrier. For example, as
science behind the ingredient activity remained much as 80% of a liquid preservative may be the
constant. A change in physical form, however, can active acid component.
often impact the activity of the ingredient on a pound While the liquid and dry forms of a preservative
per pound basis. have the same fundamental organic acid as the active
Two preservatives that are often used in the bak- ingredient, liquid preservatives are chemically some-
ing industry are calcium propionate and potassium what different from their dry counterparts due to the
sorbate. The active ingredients in these preservatives excess ions present in the dry. These ions do not have
are the organic acids propionic acid and sorbic acid, anti-microbial properties. In fact, they render the or-
respectively. To obtain a dry form of these preserva- ganic acid ineffective as a preservative at pHs above 6
tives, a saturation reaction must occur. In the case of (see the following section—Effects of pH). Ions are
calcium propionate, an excess of calcium hydroxide is merely added to preservatives to increase the pH,
reacted with liquid propionic acid to result in a dry obtain non-corrosive properties, improve water solu-
calcium propionate. Likewise, sorbic acid is reacted bility, and/or ensure the liquid acid can be formed into
with potassium hydroxide to form a dry, water-soluble a stable dry state. Because dry preservatives contain
potassium sorbate. In both cases, an excess of the an excess of ions, the pH is extremely alkaline (pH 8–
cation (calcium or potassium) is added to enhance 10) compared to a liquid preservative (pH 4–6). Thus,
water solubility and to ensure the liquid acid is the chemistry and anti-microbial activities of the two
converted into a dry powder. Only 74.5% of calcium forms are also different. This explains why a rehy-
propionate is actually the preservative propionic acid drated dry preservative does not have the same anti-
(4), assuming that the allowable 5% moisture is microbial properties as a liquid preservative.
considered (5). Similarly, 73.3% of potassium sorbate
(considering the allowable 1% moisture) is the active Effects of pH
preservative sorbic acid (4, 5).
As for dry preservatives, the active ingredient in As shown in Figure 1, pH is a means of measuring
the liquid forms is the weak acid often referred to as the acidity or alkalinity of a substance. With the
an organic acid. Because of its acidic nature, the liquid exception of parabens, all preservative ingredients
is considered corrosive by Department of Transporta- are based on organic acids (e.g., propionic or sorbic
Page 2
in shelf life is due to the reduced pH and the increased
undissociation or “activation” of the preservative in-
gredients. Because of this activation effect, pH is a
critical factor in production and in shelf life determina-
1 7 14
tion. It also explains the importance of pH consistency
and low variability for quality control measures.
ACID NEUTRAL ALKALINE
The dramatic effect of the relationship between
pH and dissociation or preservative activity can be
illustrated based on information from Table II. For
Figure 1. The pH scale
example, if a food product has a pH of 5.5, then 20%
of added propionic acid will be undissociated. If that
pH increases to 6.0, the undissociation or activity of
acids). These acids, the active components of pre- the propionic acid decreases to a mere 8.3%! Taking
servatives, can be present in intact molecular forms or this scenario one step further, the inclusion of one
they can break down (dissociate) into ions. It is the pound of calcium propionate to a product at pH 5.5
intact or undissociated forms that provide the pre- results in only 0.15 pounds of propionic acid that
servative action. As the pH decreases, the level of would be available as a preservative (74.5% propionic
intactness or undissociation increases (Table II) and acid at 20% activity and 1 pound inclusion). How-
the preservative action of the acid increases. ever, if the pH increases to 6.0, only 0.06 pounds is
It is well documented (6) that the preservative available. In other words, this small increase in pH
activity of the organic acids is dependent upon the pH would reduce the preservative’s activity by over 50%.
of the food. Each of these acids has a pKa—the pH at This could mean a tremendous difference in the
which 50% of the acid is in an undissociated form. If spoilage-free shelf life of the product.
the pH of a food product can be reduced to a level For dry preservatives, the pH ranges from 8–10.
where it approaches the pKa of the acid, the At this level, addition of the preservative to a food
preservative ingredients will be more effective. For increases the pH or the alkalinity of the finished food
example, a corn tortilla with a pH of 5.2 may have a product. Since liquid preservatives are slightly acid,
shelf life of 8 days; however, reduction of the pH to they will decrease the pH (increase acidity) of the
5.0 increases the shelf life to 20+ days. This difference product, thereby increasing the effectiveness of the
preservative. Thus, the choice of dry versus liquid
form, and the resultant effects on product pH, can
significantly impact the amount of preservative that
TABLE II must be added to maintain shelf life control.
RELATIONSHIP BETWEEN pH VALUE Solubility
AND DISSOCIATION OF ORGANIC ACIDS
In the dough making process, dry preservatives
are blended with the flour and other dry ingredients.
Undissociated pH
Water is then added to the mixer, and the dough is
Acid (%)
formed after a certain period of time. During this
Propionic Sorbic
mixing period, the granulated particles of dry pre-
Acid Acid
servatives hopefully dissolve and then disperse
99 2.87 2.75 throughout the dough matrix. The dissolution and
95 3.59 3.47 dispersion of the active preservative is critical for shelf
90 3.92 3.80 life consistency.
80 4.27 4.15 The challenge to dry preservative solubility and
70 4.50 4.38 dispersion can be viewed as a competition between
60 4.69 4.57 the preservative and other ingredients (e.g., flour) for
50 4.87 (pKa) 4.75 water. Both need water: the preservative to dissolve
and disperse, and the other ingredients for hydration.
40 5.05 4.93
The rate of water absorption by ingredients such as
30 5.24 5.12
flour has a direct impact on the time dry preservatives
20 5.47 5.35 have to dissolve and disperse.
10 5.82 5.70
1 6.87 6.75 Automation
0.5 7.17 7.05
The ideal method of incorporating liquid pre-
servatives into a processing system is to inject them
Page 3
into the water stream entering the mixer. This ensures and 0.3% potassium sorbate in the dry forms, and the
complete dispersion of the preservative throughout the resultant product pH was 5.51. When the dry pre-
dough matrix. Because water is a factor involved in servatives were replaced with 0.8% of a commercial
microbial growth, uptake of the water by the microbes liquid preservative (to provide equal shelf life), the pH
results in a concomitant absorption of the inhibiting dropped to 5.29. Based on the information in Table II,
factors (i.e., the preservatives). this translated into an 18.75% undissociation of the
Automation equipment injects the preservative dry preservatives versus a 27.5% undissociation for
into the water stream when the mixer calls for water. the liquid preservatives. In a second study, 0.3%
The water meter sends an impulse to the preservative potassium sorbate yielded a tortilla pH of 5.72. Re-
pump, which starts the pump and meters the specified placement of the sorbate with 0.2% (an amount nec-
amount of preservative into the water stream over a essary for equal shelf life) of the commercially avail-
specified amount of time. Additional components can able liquid agent caused the pH to drop to 5.45,
be added to the system to monitor the preservative which almost doubled the % undissociation value
flow through the line and to shut down the mixer if (increased from 12 to 21%). A third study decreased
flow is not detected. Empty drum indicators can also the fumaric acid (added to reduce the pH) content of
be installed to ensure that product is available for in- tortillas treated with the commercially available liquid
jection into the water when called for. Inventory con- agent to equal the pH of the potassium sorbate treat-
trol/usage can easily be monitored long term by incor- ment. In this case, the decrease in undissociation of
poration of a digital recorder or by direct connection the preservative resulted in an additional 0.1% of the
to an existing programmable controller in the manu- liquid agent required to obtain an equal shelf life.
facturing plant. These examples illustrate the fact that liquid pre-
Using application equipment to inject the pre- servatives are more active than their dry counterparts
servative into the water stream ensures not only ideal based upon the additional acidity contributed to the
dispersion but also that each batch contains the critical food product. They also reveal that reformulation
amount of preservative necessary for consistent shelf (e.g., removal of a portion of the fumaric acid) can be
life. Automation eliminates human error associated done to improve the taste of the final product.
with weighing and manual addition, as well as reduces However, changes such as this may require the liquid
human exposure to the nuisance dust of dry pre- preservative amount to be increased slightly to
servatives. compensate for the undissociation difference.
Effects of pH: Table III details the effect of fin-
USE OF PRESERVATIVES ished product pH on the amount of active preserva-
IN TORTILLAS tive acid when 1% (1 lb) of dry calcium propionate is
Tortillas can be separated into three distinct cate- added to 100 pounds of flour in the formulation of
flour tortillas. The values in the Table readily indicate
gories for preservation needs: flour tortillas, nixtamal-
the importance of pH, process control, and con-
ized or cooked corn tortillas, and masa flour tortillas.
sistency.
Each of these tortilla categories has specific preserva-
Another factor to consider is that the pH of bakery
tive needs to optimize the inhibition of microbes while
maintaining consumer taste appeal. products may change over time. A freshly manufac-
tured tortilla will have a slightly different pH than a 2-
day-old tortilla. This pH difference becomes more
Flour Tortillas
dramatic when encapsulated products such as fumaric
Flour tortillas are produced from a wheat flour acid are used. Because of the encapsulation, the re-
dough. They may be lightly leavened with a small lease of the ingredient is altered, which in turn will
amount of baking powder, or less often with a small vary the pH measurement depending upon the time it
amount of yeast. is measured after manufacturing. Industry sources
Form of preservative: Dry calcium propionate have indicated that it may take up to 3 days for some
and/or dry potassium sorbate have historically been types of encapsulated fumaric acid to disperse and
the preservatives of choice for the baking industry and stabilize the pH of a tortilla.
for flour tortillas. Due to their dry nature, they are easy Solubility: As discussed earlier, dissolution and
to weigh and add to other dry ingredients, and in- dispersion of a dry preservative are critical for shelf life
corporation into a tortilla system is easily achieved. In consistency. Flour tortilla dough has a relatively low
addition to dry forms, liquid anti-microbial agents can level of water compared to cake batter or bread
also be used in flour tortillas. dough. This low moisture content can have a negative
Studies have been conducted to investigate vari- impact on the solubility and dispersion of dry
ous approaches to controlling the shelf life of flour preservatives. In contrast to this, liquid preservatives
tortillas (7). In the first study, for example, a flour tor- are already dissolved, and they can disperse
tilla was formulated to contain 1% calcium propionate immediately in the make-up water of the dough. The
Page 4
TABLE III
a
EFFECT OF pH ON THE AMOUNT OF ACTIVE PRESERVATIVE IN FLOUR TORTILLAS
liquid preservatives are absorbed with the water into broad range of microbes and gives consistent shelf life
the flour, thus ensuring complete, even dispersion in control year round.
the food product. The other active ingredient in traditional pre-
Combinations of preservatives: Propionates servative blends, phosphoric acid, works as an acidi-
effectively inhibit most mold and rope forming bacteria fier to reduce the pH of the masa. As such, phosphoric
(bacillus) (8). However, they have a relatively low inhi- acid is not a preservative. Instead, it enhances the ef-
bition on yeasts and other types of bacteria. Sorbate is fectiveness of the preservative ingredients by reducing
often used in conjunction with propionate in flour the pH level in the food product.
tortillas to form a synergy that enhances the effective- Dry preservatives are not recommended for addi-
ness of both ingredients as well as inhibiting yeast. tion to masa dough. The dry particles of preservative
stick to the dough and do not disperse evenly. This
Corn Tortillas will cause preservative hot spots and spoilage of ran-
dom packages.
Historically, all corn tortillas have been treated
b) pH: As discussed earlier, the lower the pH of a
alike for shelf life extension. However, nixtamalized
food product, the more effective the preservative in-
corn tortillas and masa flour tortillas have very differ-
gredients. During the nixtamalizaton process, corn is
ent characteristics and, ultimately, very different pre-
cooked in lime water. This process increases the pH of
servative needs.
the corn to an alkaline value (pH above 7). The
Nixtamalized corn tortillas: In the nixtamali- washing step that follows cooking and steeping of the
zation process, corn is cooked in lime (calcium corn removes the excess lime and reduces the pH level.
hydroxide) water, steeped, washed to remove excess If the wash step is incomplete or omitted, the pH of the
lime, and then stone ground. Nixtamalized corn tortil- ground corn will be alkaline and/or variable. In this
las are produced directly from this ground material or situation, the amount of preservative must be increased
masa dough. to obtain the critical shelf life pH. If the pH factor is not
a) Preservative choices: Traditional preserva- met, the resulting product shelf life will be reduced.
tives for nixtamalized corn tortillas contain blends of c) Preservative application: To obtain maxi-
propionic acid and phosphoric acid. The active mum effectiveness, a preservative must be evenly dis-
preservative ingredient, propionic acid, is most effec- tributed into the masa dough. Even distribution will
tive against mold and some types of bacteria. High reduce the number of packages that randomly spoil
levels of this type of preservative must be used to and will also even out the taste of the tortillas.
control all types of spoilage and fermentation. The Application of a liquid preservative at the stones
most effective preservative product with a lower inclu- will assist with the distribution of the preservative.
sion rate will contain a duel preservative system that However, hot spots may still occur. The ideal method
incorporates propionic acid, as well as a second pre- for preservative dispersion is incorporation of the liq-
servative, such as methyl or propyl paraben or sorbic uid preservative at the stones and then blending the
acid. This type of blend forms a synergy that inhibits a masa thoroughly in a conventional mixer. Figure 2
Page 5
4.5 100% 10 100%
4 9
80% 8 80%
3.5
Frequency 7 Frequency
3 Cumulative %
Cumulative (%)
Cumulative (%)
Cumulative %
6 60%
Frequency
60%
Frequency
2.5
5
2
40% 4 40%
1.5
3
1
20% 2 20%
0.5 1
0 0% 0 0%
5.6 5.5 5.7 5.8 More 5.3 5.4 5.4 5.5 5.3 5.6 5.7 5.8 More
pH pH
illustrates the pH range of masa with preservative second preservative ingredient, such as potassium
added at the stones compared to masa that was sorbate, benzoic acid, or methyl or propyl paraben.
blended for 10 minutes after the addition. The pH The amount and type of preservative applied to the
range was dramatically reduced by the mixing step. flour determines the shelf life of the tortilla. For exam-
The resulting tight pH range leads to a more consistent ple, a short shelf life (3–5 days) will only require
performance of the inhibitors and, thereby, improves propionate and fumaric acid. However, a longer shelf
the shelf life uniformity of the packaged tortillas. life (9–11 days) will necessitate the addition of a sec-
A variety of application pumps are available for ond preservative ingredient, such as sorbate, benzoic
preservative addition at the stones or grinder. The acid, or parabens.
ideal application method that will enhance dispersion The shelf life of masa flour tortillas may also be
is to inject the preservative into the water feeding the extended by the addition of liquid preservatives into
stones. It is also recommended that the pump be tied the make-up water. Historically, these preservatives
to the grinder motor so the preservative is automati- have been based upon propionic acid as a preserva-
cally turned on and off with the stones. tive and phosphoric acid as the acidifier. This is the
Masa flour tortillas: Masa flour is a product same type of mixture used for nixtamalized tortillas.
that is commercially produced from nixtamalized corn. These blends are corrosive, and may give an off taste
Following the cooking, steeping, rinsing, and grinding and odor to the tortillas. Since masa flour consistently
steps, the nixtamilized masa dough is dried and delivers a slightly acid pH (approximately 5.8–6.3), a
ground to a flour that has a moisture content of about less acidic preservative blend can also be effective.
10%. Because this product is commercially produced, This type of blend reduces the preservative taste and
the cooking and washing variables are carefully odor, and is considered non-corrosive. Non-corrosive
controlled. As a result, masa flour has a relatively liquid preservatives contain sodium propionate and a
consistent pH level. second preservative ingredient, such as methyl or
Due to a variety of differences, corn tortillas made propyl paraben or potassium sorbate. This duel com-
from masa flour have different preservative needs bination of preservatives effectively inhibits the growth
than nixtamalized tortillas. of mold, yeast, and bacteria, which may cause spoil-
a) Preservative choices: Masa flour is available age or fermentation problems. In addition, a non-
with or without preservatives and acidifiers. Preserved corrosive product improves employee safety and
masa flour contains fumaric or phosphoric acid as an eliminates many of the transportation and storage
acidifier, and calcium or sodium propionate and/or a problems associated with corrosive products.
Page 6
b) Preservative application: Liquid preserva- ered. This will assist in determining the appropriate
tives may be measured and added by hand to the anti-microbial agents to be used.
make-up water, or they can be automatically injected
with the same type of equipment discussed earlier (see Production Trials
Automation section, pages 3 and 4). Automation
Once the available preservative products have
equipment not only eliminates the human error in
been identified and a supplier has been chosen, a
weighing and addition, but also ensures the critical
manufacturing test should be conducted. This will de-
preservative ingredient is added. If application automa- termine the amount of preservative required, based on
tion is not an option, a non-corrosive type of liquid pre- the formulation and manufacturing conditions, to ob-
servative should be used to improve employee safety.
tain the desired shelf life of the tortillas. After the cor-
rect amount of preservative has been identified, a
SELECTING A LIQUID PRESERVATIVE
second production trial should be performed to con-
Liquid preservatives have a wide range of appli- firm that the application rate provides the desired shelf
cations and are easy to use. For these and other rea- life.
sons, they are often chosen as shelf life control agents
for tortillas and other products. Sensory Evaluation
Products made during the second production trial
Factors to Consider
can be evaluated to determine the effect of the pre-
When selecting a liquid preservative and a servative on the taste of the product. When conduct-
supplier of that preservative, the following factors ing these taste comparisons, it is recommended that
should be considered: non-production employees be used as panel mem-
• Ingredient content: Is a single or a duel content bers. Production employees know the exact taste of
preservative required? their current tortilla, and as a result, their opinions
may be biased. A variety of taste panel methods are
• Characteristics: Does the preservative have a available for use in comparisons. These include the
corrosive (pH <4) or non-corrosive nature, 2-Choice taste test, which merely asks each panel
and what is its impact on safety? member to indicate the preferred of two products,
• Concentration: Concentrated preservatives cost and the 5-Point Hedonic taste test, in which the
more on a per pound basis. However, a lesser panelists rank the degree of like or dislike. Results of
amount of concentrated preservative is re- the taste comparisons, when used in conjunction with
quired per pound of food product. This reduces other factors listed above, will help to establish the
warehouse space needs as well as freight and suitability of a preservative for shelf life control of a
handling costs. tortilla system.
• Quality and consistency: What is the supplier’s
sophistication of quality control and production SUMMARY
methods (as measured by statistical process Preservatives are agents used to control microbial
control charts, analytical monitoring of pre- growth in a variety of food products. While liquid and
servative ingredients, and computerized lot and dry forms of preservatives are available, differences
ingredient tracking)? between the two forms do exist, and these may have
• Availability: What options does a supplier an impact on the functionality of these anti-microbial
provide for handling a customer’s emergency agents in particular food systems. Another important
shortage? factor is the pH of the food, since lower pH levels
• Automated application equipment: What types (more acidic) lead to a decrease in the dissociation of
of equipment are available? How reliable and preservatives and, thereby, increase their effective-
easy to use are they? ness.
Tortillas are products in which preservatives can
• Technical service: Does the supplier provide
have a substantial impact on shelf life. Because of the
technical support? What is their typical re-
sponse time to customer complaints? differences in ingredients and processes, the various
types of tortillas (flour, nixtamalized corn, and masa
• Research and development: Does the supplier flour corn) have differing requirements for the types of
work to continuously improve their product preservative agents used.
offerings? An optimized preservative product in combination
The above factors and how they relate to the with a preservative program that ensures sanitation
products and processing methods for which the pre- and tight quality control specifications will deliver a
servatives are being chosen should be carefully consid- product with consistent shelf life control.
Page 7
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3. DAVIDSON, P.M. and BRANEN, A.L.
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Inc., New York, NY, 1993.
4. MERCK. The Merck Index, 10th ed., Merck & Co.,
Inc., Rahway, NJ, 1983.
5. FCC. Food Chemicals Codex, 4th ed., National
Academy Press, Washington, DC, 1996.
6. MATZ, S.A. Bakery Technology and Engineering,
3rd ed., Van Nostrand Reinhold, New York, NY,
1992.
7. ROLOW, A. Effectiveness of Shield NA Plus Liq-
uid in Flour Tortillas—Summary of 3 Production
Trials. Kemin Americas, Inc., 1998.
8. LEWIS, R.J. Sr. Food Additives Handbook, Van
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