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199 views8 pages

Fundamentals PDF

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Ali Yıldırım
Copyright
© © All Rights Reserved
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D DECAGON

DEVICES

Fundamentals of
Water Activity

I
“ t is now generally accepted that aw is more closely related to
the physical, chemical, and biological properties of foods and
other natural products than is total moisture content. Specific
changes in color, aroma, flavor, texture, stability, and
acceptability of raw and processed food products have been
associated with relatively narrow aw ranges.”
—Rockland LB & Nishi SK, Food Tech 34:42-59 (1980).

CONTENTS
What is Water Activity?
Page 2-3
n Definition
n Measurement Methods

Water activity for product


safety and quality
Page 4-5
n Microbial Growth
n Chemical/Biochemical Reactivity
n Physical Properties
n Moisture Migration

Government Compliance
Page 6–7

Microbial Growth Limits Table


Page 8

1
What is Water Activity?

W
ater is recognized as being Water Activity is Most humidity of air surrounding the
very important, if not Relevant for Quality and sample in a sealed measurement
critical, to the stability of Safety Issues chamber. Multiplication of water
most products. Controlling the water Another more important type of activity by 100 gives the equilibrium
within a product, by some method of water analysis is water activity (aw). relative humidity (ERH) in percent.
drying or by chemically/structurally Water activity describes the energy
binding (salting or sugaring) has long status or escaping tendency of the aw = p/po = ERH (%) / 100
been used by man for preservation. water in a sample. It indicates how
This not only controls microbial tightly water is “bound,” structurally As described by the above equation,
spoilage, but also chemical and or chemically, in products. Both the water activity is a ratio of vapor
physical stability. water content and the water activity pressures and thus has no units. It
of a sample must be specified to fully ranges from 0.0aw (bone dry) to
Water Content Alone is describe its water status. However, 1.0aw (pure water).
Not a Reliable Predictor water activity is the property most
Traditionally, discussions about relevant for quality and safety issues. “Bound” Water is
water in products or ingredients focus Water activity is closely related to the Not Totally Immobilized
on moisture or water content, which partial specific Gibbs free energy of Water activity is sometimes
is a quantitative or volumetric the system. Thus, water activity is a described in terms of the amounts of
analysis that determines the total thermodynamic concept and has “bound” and “free” water in a
amount of water present. Water requirements for measurements. product. Although these terms are
content of a product is a familiar These requirements are that the easier to conceptualize, they fail to
concept to most people. One system be in equilibrium, the define all aspects of the concept of
measures the water content by loss on temperature defined, and a standard water activity. “Free” water is not
drying, infrared, NMR or Karl Fisher state specified. Pure water is taken as subjected to any force that reduces its
titration. Moisture content the reference or standard state from energy; therefore, all water in food is
determination is essential in meeting which the energy status of water in “bound” water. The issue is not
product nutritional labeling food systems is measured. The Gibbs whether water is “bound,” but how
regulations, specifying recipes and free energy of free water is zero; thus, tightly it is “bound”. Water activity
monitoring processes. However, the water activity is 1.0. is a measure of how tightly water is
water content alone is not a reliable “bound” and related to the work
predictor of microbial responses and Water Activity is a Ratio required to remove water from the
chemical reactions in materials. of Vapor Pressures system. Water that is “bound”
Water activity is the ratio of the should not be thought of as totally
Chemically Bound Water is vapor pressure of water in a material immobilized. Microbial and chemical
Unavailable to Microbes (p) to the vapor pressure of pure processes are related to this “bound”
The limitations of water content water (po) at the same temperature. energy status in a fundamental way.
measurement as an indicator of safety Relative humidity of air is the ratio of Because water is present in varying
and quality are attributed to the vapor pressure of air to its energy states, analytical methods that
differences in the intensity which saturation vapor pressure. When attempt to measure total moisture in
water associates with other vapor and temperature equilibrium samples don’t always agree or relate
components in the product. The are obtained, the water activity of the to safety and quality. Water activity
water content of a safe product varies sample is equal to the relative tells the real story.
from product to product and from
formulation to formulation. One safe,
stable product might contain 15% AquaLab
water while another containing just
8% water is susceptible to microbial
growth. Although the wetter product
contains proportionally more water,
its water is chemically bound by
other components, making it
unavailable to microbes. Using only
water content values, it’s impossible
to know how “available” the water
in the product is to support microbial
growth or influence product quality. AquaLab Lite

2
 “There is now wide agreement that a w is the most useful expression of the water requirements for microbial growth and
enzyme activity. The alternatives of solute concentration and water content have been shown very clearly by Scott (1962) to
be inadequate for describing the availability of water for the multiplication of certain bacteria.”
Troller JA, & Christian JHB, Water Activity—Basic Concepts. in Water Activity and Food, (Academic Press, New York, 1978),
Chap. 1, pp. 1–12.
“Bound” or “Free” Water are products and enforce government Water Activity Measurement
Not Very Useful Descriptions regulations. Two different types of in Less than 5 Minutes
There are several factors (osmotic, water activity instruments are The major advantages of the chilled
matrix, and capillary) that control commercially available. One uses mirror dewpoint method are speed
water activity in a system. It is a chilled mirror dewpoint technology and accuracy. Chilled mirror
combination of these factors in a while the other utilizes relative dewpoint is a primary approach to
product that reduces the energy of the humidity sensors that change measurement of relative humidity
water and thus reduces the vapor electrical resistance or capacitance. based on fundamental
pressure above the sample as Each has advantages and thermodynamic principles. Chilled
compared to pure water. Due to disadvantages. The methods vary in mirror instruments make accurate
varying degrees of osmotic and accuracy, repeatability, speed of (±0.003aw) measurements in less than
matrix interactions, water activity measurement, stability in calibration, 5 minutes. Since the measurement is
describes the continuum of energy linearity, and convenience of use. based on temperature determination,
states of the water in a system rather calibration is unnecessary, but
than a static “boundness”. “Bound” Chilled Mirror Dewpoint running a standard salt solution
or “free” are not a very useful In a chilled mirror dewpoint system, checks proper functioning of the
description since it is an attempt to a sample is placed in a sample cup instrument. If there is a problem, the
classify a continuum in terms of which is sealed against a sensor mirror is easily accessible and can be
discrete states. block. Inside the sensor block is a cleaned in a few minutes. For some
dewpoint sensor, an infrared applications, fast readings allow
Two Methods of thermometer, and a fan. The manufacturers to perform at-line
Water Activity Instruments dewpoint sensor measures the monitoring of a product’s water
are Available dewpoint temperature of the air, and activity.
There is no device that can be put the infrared thermometer measures
into a product that directly measures the sample temperature. From these Electric Hygrometers
the water activity. Rather, aw is measurements the relative humidity Other water activity instruments use
measured with an indirect method. of the headspace is computed as the resistance or capacitance sensors to
Water activity is measured by ratio of dewpoint temperature measure relative humidity. These
equilibrating the liquid phase water saturation vapor pressure to sensors are made from a hygroscopic
in the sample with the vapor phase saturation vapor pressure at the polymer and associated circuitry that
water in the headspace of a closed sample temperature. When the water gives a signal relative to the
chamber and measuring the relative activity of the sample and the relative equilibrium relative humidity (ERH).
humidity of the headspace. Methods humidity of the air are in equilibrium, Commercially available instruments
for water activity determinations are the measurement of the headspace measure over the entire aw range with
detailed in the Official Methods of humidity gives the water activity of an accuracy of ±0.015aw. Since these
Analysis of AOAC International the sample. The fan is to speed instruments relate an electrical signal
(1995). New instrument technologies equilibrium and to control the to relative humidity, the sensor must
have vastly improved speed, accuracy boundary layer conductance of the be calibrated with known salt
and reliability of measurements. dewpoint sensor. standards. In addition, the ERH is
Reliable laboratory instrumentation equal to the sample water activity
is required to guarantee the safety of only as long as the sample and sensor
temperatures are the same. Accurate
measurements require good
temperature control or measurement.
SafeStorage Advantages of capacitance sensors
include simple design and inexpensive
implementation. 

Pawkit
D DECAGON
DEVICES

3
Water activity for
product safety and quality. D DECAGON
DEVICES

W
ater activity’s usefulness as designing a product below a critical lowered, the rate of
a quality and safety aw level provides an effective means chemical degradative
measurement was to control growth. Water may be reactions decreases.
suggested when it became evident present, even at high content levels, in
moisture content could not a product, but if its energy level is Physical Properties
adequately account for microbial sufficiently low the microorganisms Besides predicting the
growth fluctuations. Water activity is cannot remove the water to support rates of various chemical
a measure of the energy status of the their growth. This ‘desert-like’ and enzymatic reactions,
water in a system. The water activity condition creates an osmotic water activity affects the
(aw) concept has served the imbalance between the textural properties of
microbiologist and food technologist microorganisms and the local foods. Foods with high
for decades and is the most environment. Consequently, the aw have a texture that is
commonly used criterion for safety microbes cannot grow and its described as moist, juicy,
and quality. Its usefulness cannot be numbers will decline until it tender, and chewy. When
denied. eventually dies. the water activity of
these products is
Predicting Safety Limiting lowered, undesirable
and Stability Microorganism Growth textural attributes, such
Water activity While temperature, pH, and several as hardness, dryness,
predicts safety and other factors can influence whether staleness, and toughness,
stability with respect an organism will grow in a product are observed. Low aw
to microbial growth, and the rate at which it will grow, products normally have
chemical and water activity is often the most texture attributes
biochemical reaction important factor. Water activity may described as crisp and
rates, and physical be combined with other preservative crunchy, while these
properties. Figure 1 factors (hurdles), such as products at higher aw
shows stability in temperature, pH, redox potential, levels change to soggy
terms of microbial etc., to establish conditions that texture. Critical water
growth limits and rates of inhibit microorganisms. The water activities determine
degradative reactions as a function of activity level that limits the growth of where products become unacceptable
water activity. Therfore, by the vast majority of pathogenic from a sensory standpoint.
measuring and controlling the water bacteria is 0.90aw, 0.70aw for
activity, it is possible to: a) predict spoilage molds, and the lower limit Caking, Clumping, Collapse
which microorganisms will be for all microorganisms is 0.60aw. and Stickiness
potential sources of spoilage and Table 1 (back page), lists the water Water activity is an important factor
infection, b) maintain the chemical activity limits for growth of affecting the stability of powders and
stability of products, c) minimize microorganisms significant to public dehydrated products during storage.
nonenzymatic browning reactions health and examples of products in Controlling water activity in a
and spontaneous autocatalytic lipid those ranges. powder product maintains proper
oxidization reactions, d) prolong the product structure, texture, stability,
activity of enzymes and vitamins, and Chemical/Biochemical density, and rehydration properties.
e) optimize the physical properties of Reactivity Knowledge of the water activity of
products such as moisture migration, Water activity influences not only powders as a function of moisture
texture, and shelf life. microbial spoilage but also chemical content and temperature is essential
and enzymatic reactivity. Water may during processing, handling,
Microbial influence chemical reactivity in packaging and storage to prevent the
Growth different ways; it may act as a deleterious phenomenon of caking,
Microorganisms solvent, reactant, or change the clumping, collapse and stickiness.
have a limiting water mobility of the reactants by affecting Caking is water activity, time, and
activity level below the viscosity of the system. Water temperature dependent and is related
which they will not activity influences nonenzymatic to the collapse phenomena of the
grow. Water activity, not moisture browning, lipid oxidization, powder under gravitational force.
content, determines the lower limit of degradation of vitamins and other
“available” water for microbial nutrients, enzymatic reactions, Moisture Migration
growth. Since bacteria, yeast, and protein denaturation, starch Because water activity is a measure
molds require a certain amount of gelatinization, and starch of the energy status of the water,
“available” water to support growth, retrogradation (see Figure 1). differences in water activity between
Typically, as the water activity level is components is the driving force for

4
 “The practical applications of a w throughout the food industry have generated
creative new food products worth many billions of dollars since the 1960s. Perhaps
of even greater potential value is the pool of basic information about a w and its
connection to moisture relations and food qualities that has been generated since
the 1960s.”
Bone DP, Practical Applications of Water Activity and Moisture Relations in Foods. in
Water Activity: Theory and Applications to Food, L. B. Rockland, L. R. Beuchat, Eds.
(Marcel Dekker Inc., New York, 1987), Chap. 15, pp. 369-395.

Figure 1
Water Activity - Stability Diagram

Loss of Crispness Non-PHF PHF

Powder Caking

Lip
Relative Reaction Rate
Collapse

id
Ox
Moisture Content
Browning

ida
Reactions

tio
n

otherm
Sorption Is
Moisture
vity
e Acti

ria
st
Enzym Grow
th

cte
Ye
Mold

Ba
!
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Water Activity

 Modern water activity instruments Water Adjusts Between ingredients at the same moisture
ensure safe quality food products. Materials Until Water content may not be compatible when
Activity Equilibrium mixed. If two materials of differing
moisture migration as the system Differences in water activity levels water activities but the same water
comes to an equilibrium. Thus, water between components or a component content are mixed, the water will
activity is an important parameter in and environmental humidity are a adjust between the materials until an
controlling water migration of driving force for moisture migration. equilibrium water activity is
multicomponent products. Some Knowledge of whether water will obtained.
foods contain components at absorb or desorb from a particular
different water component is essential to prevent Shelf-life/Packaging
activity levels, such as degradation, especially if the Water activity is a critical factor in
filled snacks or substance is moisture sensitive. For determining the shelf life of products.
cereals with dried example, if equal amounts of Critical upper and lower water
fruits. By definition, component 1 at 2% and component activity levels can be established with
water activity dictates 2 at 10% moisture content must be respect to microbial, texture, flavor,
that moisture will blended together, will there be appearance, aroma, nutritional, and
migrate from a region moisture exchange between the cooking qualities for food products.
of high aw to a region of lower aw, components? The final moisture Rates of exchange of moisture
but the rate of migration depends on content of the blended material through the package and the rate of
many factors. Undesirable textural would be 6%, but did any moisture change in aw of the food towards a
changes can result from moisture exchange between component 1 and critical limit will determine the shelf
migration in multicomponent foods. 2? The answer depends on the water life of a product. Knowledge of the
For example, moisture migrating activities of the two components. If temperature, ambient relative
from the higher aw dried fruit into the the water activities of the two humidity and critical aw values will
lower aw cereal causes the fruit to components are the same, then no aid in selection of a package with the
become hard and dry while the cereal moisture will exchange between the correct barrier properties to optimize
becomes soggy. two components. Also, two quality and shelf life. 

5
Government Compliance

T
he U.S. food, drug, and food supply. Consequently, a science which is below the pH for proteolytic
cosmetic laws are intended to based system, Hazard Analysis and Clostridium botulinum growth and
assure the consumer that Critical Control Points (HACCP), has toxin production.
foods are pure, wholesome, safe to been created to improve food safety
eat, and produced under sanitary and reduce the incidence of New Scientific Based Criteria
conditions; that drugs and medical foodborne illness. The 2005 version of the Food Code
devices are safe and effective for their updates the definitions of PHF by
intended uses; that cosmetics are safe In-process Detection using a scientific based criteria that
and made from appropriate HACCP is a way for industry to considers the interaction of aw and
ingredients; and that all labeling and control and prevent problems, and pH in determining if a food is
packaging is truthful, informative, ensure safe food by controlling the designated as a non-PHF/non-TCS
and not deceptive. Modern scientific production process from beginning to food. Interaction Tables A & B
methods are required to enforce the end, rather than detecting problems consider the interaction of aw and pH
Federal Food, Drug, and Cosmetic at the end of the line. It identifies under certain conditions of heat-
Act. Laws to ensure the where hazards might occur in the treatment and packaging. The hurdle
wholesomeness of foods and the food production process and puts effect will control or eliminate
safety and efficacy of drugs would be into place actions to prevent the pathogens that would otherwise be
impractical without reliable methods hazards from occurring. For example, ineffective when used alone. The
of laboratory analysis to determine a target water activity must be effect of a heat treatment which
whether products are up to a established to prevent hazardous destroys vegetative cells and the effect
standard. organisms from growing. By of packaging which prevent
controlling major food risks, such as recontamination is considered.
Good Manufacturing Practice microbiological, chemical and
The United States has one of the physical contaminants, the industry 0.85 or Less aw Will Not
safest food supplies of any country in can better assure consumers that its Support Pathogenic
the world. The FDA’s Good products are safe. Bacterial Growth
Manufacturing Practice Regulations The USDA and FSIS also use water
incorporates water activity guidelines Potentially Hazardous Food activity in Generic HACCP Model 10
in defining food safety regulations. The term potentially hazardous food for Heat-treated, Shelf-stable Meat
GMP regulations detail the specific (PHF) was developed by the U.S. and Poultry Products. The science
requirements and practices to be Public Health Service during the last states and verifies that all pathogenic
followed by industry to assure that half of the twentieth century to bacteria stop growing at a water
foods are produced under sanitary regulate perishable food. Potentially activity of 0.86. The model states that
conditions and are pure, wholesome, hazardous food means a food that “Manufacturers should not use the
and safe to eat. Specific parts and requires time/temperature control for moisture protein ratio (MPR) as a
paragraphs of applicable GMP safety (TCS) to limit pathogenic measure of proper drying for shelf-
regulations from Title 21 of the Code microorganism growth or toxin stability or safety. It is product water
of Federal Regulations use aw in formation. Foods were considered activity that is best correlated to
relation to control measures and food non-PHF when their aw ) 0.85, which inhibition of each pathogen’s
safety. However, neither GMP’s alone is below the water activity for growth.” Thus, if you produce jerky
nor activities of regulatory agencies Staphylococcus aureus growth and to a water activity of 0.85 or less,
alone can guarantee a completely safe toxin production or the pH ) 4.6, then the product will not support the

6
 “Water activity plays an important role in the safety, quality, processing, shelf life, texture and sensory properties of foods.”
Fontana AJ & Campbell CS, Water Activity. in Handbook of Food Analysis, Physical Characterization and Nutrient Analysis, L.
M. L. Nollet, Ed. (Marcel Dekker, New York, 2004), Chap. 3, pp. 39-54.

growth of any pathogenic bacteria. Interaction Table A


Drying your product to a water
activity of 0.80 or less does not make Table A. Interaction of pH and aw for control of spores in food heat-
the product any safer. The product treated to destroy vegetative cells and subsequently packaged.
will have less consumer appeal
aw Values pH Values
(because it will be tougher and
chewier) and because jerky is sold on 4.6 or less > 4.6 – 5.6 > 5.6
a weight basis, you will be losing 0.92 or less Non-PHF*/non- Non-PHF/non- Non-PHF/non-
profit. TCS** TCS TCS
> 0.92 – 0.95 Non-PHF/non- Non-PHF/non- PA***
Pharmaceutical TCS TCS
and Cosmetics > 0.95 Non-PHF/non- PA PA
Currently there are no water activity TCS
regulations for pharmaceutical or * PHF means “Potentially Hazardous Food”
cosmetic products. Although, there is
** TCS means “Time/Temperature Control for Safety Food”
a proposed USP (United States
*** PA means “Product Assessment Required”
Pharmacopeial) Method <1112>
using water activity. USP Method
 Table A can be used to determine if a food which is heat-treated and
<1112> Microbiological Attributes of
Nonsterile Pharmaceutical Products – packaged is PHF, Non-PHF or Requires Product Assessment. Food must meet
Application of Water Activity cooking requirements of Food Code section 3-401.11 (no partial cooks) to
Determination provides guidance on
eliminate vegetative pathogens. Spore forming pathogens are the only
the influence of water activity as it
pertains to product formulation remaining biological hazards of concern. Food is packaged to prevent re-
susceptibility to microbial contamination. Therefore, higher pH & a w can be safely tolerated.
contamination. The chapter discusses
the potential for improving product
preservation by maintaining low
Interaction Table B
water activity. The determination of
the water activity of nonsterile
Table B. Interaction of pH and aw for control of vegetative cells and
pharmaceutical dosage forms aids in spores in food not heat-treated or heat-treated but not packaged.
the decisions about the following:
aw Values pH Values

 Optimizing product formulations < 4.2 4.2 – 4.6 > 4.6 – 5.0 > 5.0
to improve antimicrobial effectiveness < 0.88 Non-PHF*/non- Non-PHF/non- Non-PHD/non- Non-PHF/non-
of preservative systems. TCS** TCS TCS TCS
0.88 – 0.90 Non-PHF/non- Non-PHF/non- Non-PHF/non- PA***
TCS TCS TCS
 Reducing the degradation of active
pharmaceutical ingredients within > 0.90 – 0.92 Non-PHF/non- Non-PHF/non- PA PA
TCS TCS
product formulations susceptible to
> 0.92 Non-PHF/non- PA PA PA
chemical hydrolysis. TCS
* PHF means “Potentially Hazardous Food”
 Reducing the susceptibility of ** TCS means “Time/Temperature Control for Safety Food”
formulations (especially liquids, *** PA means “Product Assessment Required”
ointments, lotions, and creams) to
microbial contamination.  Table B can be used to determine if a food which is not heat-treated or heat-

treated but not packaged is PHF, Non-PHF or Requires Product Assessment.


 Providing a tool for the rationale
for reducing the frequency of Food not heat-treated may contain vegetative cells and pathogenic spores.
microbial limit testing and screening Food that was heat-treated but not packaged may become re-contaminated.
for objectionable microorganisms for
pH values considered in Table B must include 4.2 because Staphylococcus
product release and stability testing
using methods contained in the aureus can grow at that level.

D
general test chapter Microbial Limit
Tests <61>. 
DECAGON
DEVICES
7
 “The importance of the water activity—moisture content concept of foods cannot be overemphasized. More importantly, the
value of water activity has been shown to control the stability of dehydrated and semi-moist foods.”
Labuza TP, Sorption Phenomena in Foods: Theoretical and Practical Aspects. in Theory, Determination and Control of Physical
Properties of Food Materials, C. Rha, Ed. (D. Reidel Publishing Co., Dordrecht-Holland, 1975), Chap. 10, pp. 197-219.

aw Microorganism
Yeast Typical Products
Bacteria Molds
Clostridium botulinum E
0.97 Pseudomonas fluorescens — — Fresh meat, fruit, vegetables,
canned fruit, canned vegetable,
Escherichia coli — —
Clostridium perfringens low-salt bacon, cooked
0.95 Salmonella spp. sausages, nasal spray, eye drops
Vibrio cholerae
0.94 Clostridium botulinum A, B Stachybotrys atra —
Vibrio parahaemolyticus
0.93 Bacillus cereus Rhizopus nigricans — Some cheeses, cured meat
(ham), bakery goods,
0.92 Listeria monocytogenes — — evaporated milk, Oral liquid
suspensions, topical lotions
0.91 Bacillus subtilis — —
Staphylococcus aureus Saccharomyces
0.90 Trichothecium roseum cerevisiae
(anaerobic)
0.88 — — Candida
Staphylococcus aureus
0.87 — —
(aerobic) Sweetened condensed milk,
0.85 — Aspergillus clavatus — aged cheeses (cheddar),
fermented sausage (salami),
0.84 — Byssochlamys nivea — dried meats (jerky), bacon,
most fruit juice concentrates,
Penicillium expansum chocolate syrup, fruit cake,
Penicillium islandicum Debarymoces hansenii fondants, Cough syrup, oral
0.83 — Penicillium viridicatum analgesic suspensions
Aspergillus fumigatus
0.82 — Aspergillus parasiticus —
Penicillium cyclopium
0.81 — —
Penicillium patulum
0.80 — — Saccharomyces bailii

0.79 — Penicillum martensii —

0.78 — Aspergillus flavus —


Jam, marmalade, marzipan,
Aspergillus niger glace fruits, molasses, dried
0.77 — Aspergillus ochraceous —
figs, heavily salted fish
0.75 — Aspergillus restrictus —
Aspergillus candidus
0.71 — Eurotium chevalieri —

0.70 — Eurotium amstelodami —


Dried fruit, corn syrup,
0.62 — — Saccharomyces rouxii licorice, marshmallow,
chewing gums, dried pet foods
0.61 — Monascus bisporus —

0.60 No microbial proliferation


Caramels, toffees, honey,
0.50 No microbial proliferation noodles, topical ointment
Whole egg powder, cocoa,
0.40 No microbial proliferation
liquid center cough drop
Crackers, starch based snack
0.30 No microbial proliferation foods, cake mixes, vitamin
tablets, suppositories
Boiled sweets, milk powder,
<0.20 No microbial proliferation infant formula

D DECAGON
DEVICES
950 NE Nelson Court
509-332-2756
fax 509-332-5158
[email protected]
Pullman, Washington 99163 ©2006 DECAGON Printed in USA www.decagon.com/aqualab/

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