FEATURE

Understanding the Importance of Water Activity in Food

A. J. F ONTANA , J R .
Decagon Devices, Inc. Pullman, WA

nderstanding the role of water activity in food is important for food quality, stability, and safety. Water activity is an important property that can be used to predict food stability and safety with respect to microbial growth, rates of deteriorative reactions, and physical properties. Throughout history the importance of controlling water in food to preserve and control food quality by drying, freezing, or adding sugar or salt has been recognized. Water activity is a measure of the energy status of the water in a system (or the degree to which water is bound) and, hence, its availability to act as a solvent and participate in chemical and biochemical reactions and growth of microorganisms. The concept of water activity has been incorporated by various regulatory agencies in defining safety regulations regarding growth of undesirable microorganisms, definitions of potentially hazardous foods, critical control points, standards for several preserved foods, and packaging requirements. Two basic properties of water can be measured. First, water content describes the total amount of water present in a food system. Second, water activity (a w ) describes the energy status or escaping tendency of the water in a product. The water activity of a product is equal to the relative humidity of the air in equilibrium with the product in a sealed measurement chamber. Both the water content and activity of a product must be specified to fully describe its water status. However, water activity is the property most important in food quality and safety issues.

Figure 1 shows food stability in terms of rates of degradative reactions as a function of water activity (1). Water activity predicts food safety and stability with respect to microbial growth, chemical and biochemical reaction rates, and physical properties. By measuring and controlling water activity in foodstuffs, it is possible to 1) predict which microorganisms will be potential sources of spoilage and infection, 2) maintain the chemical stability of foods, 3) minimize nonenzymatic browning reactions and spontaneous autocatalytic lipid oxidation reactions, 4) prolong the desired activity of enzymes and vitamins in food, and 5) optimize the physical properties of foods, such as texture and shelf life. Each of these areas will be discussed in detail. Microbial Safety One purpose of food safety is to prevent growth of and toxin production by harmful microorganisms. According to the 1995 trends shown in a U.S. survey, American consumers confidence in the safety of its food supply has increased. In fact, 77% of shoppers are now completely or mostly satisfied that supermarket foods are safe (2). However, spoilage and bacterial contamination were identified as concerns. Scott (3) showed that microorganisms have a limiting water-activity level below which they will not grow. Water activity (a w ), not water content, determines the lower limit of available water for microbial growth. The lowest a w levels at which the vast majority of food-spoiling bacteria will

grow is 0.90. Staphylococcus aureus under anaerobic conditions is inhibited at an a w of 0.91, but under aerobic conditions the inhibitory a w level is 0.86. The a w limit for mold and yeast growth is 0.61, whereas mycotoxigenic molds have a lower limit for growth at an a w of 0.78 (4). Table I lists the water activity limits for growth of microorganisms significant to public health and examples of foods that generally contain microorganism levels within these ranges. In addition to the relationship between microbial growth and water activity, a number of other aspects of food microbiology are influenced by water activity. The effect of a w on sporulation, germination, and mycotoxin production of microorganisms is complex (5). Generally for yeast, a higher a w level is required for sporulation than for spore germination. The minimum aw level for toxin production is generally higher than the minimum a w level necessary for growth. Chemical and Biochemical Reactivity Water activity influences not only microbial spoilage but also chemical and enzymatic reactions. Water may act as a solvent or reactant or change the mobility of the reactants by affecting the viscosity of the food system (6). Water activity influences the rate and extent of nonenzymatic browning, lipid oxidation, degradation of vitamins,
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Publication no. W-1999-1214-01F. 2000 American Association of Cereal Chemists, Inc.

enzymatic reactions, protein denaturation, starch gelatinization, and starch retrogradation. The rate of nonenzymatic browning increases with increasing aw, reaching a maximum at aw ranging from 0.6 to 0.7 (Fig. 1). Lipid oxidation rate is at its minimum when aw has an intermediate range and increases at both high and low aw levels, although due to different mechanisms. These

reactions result in the formation of highly objectionable flavors and odors. Watersoluble vitamin degradation in food systems increases with increasing aw levels (7). Enzyme and protein stability is influenced significantly by water activity due to their relatively fragile natures. Most enzymes and proteins must maintain conformation to remain active. Maintaining critical aw levels to prevent or entice conforma-

tional changes is important to food quality. Most enzymatic reactions are slowed at water activities below 0.8, but some reactions occur even at very low aw levels, such as 0.20.3. Water activity also influences the gelatinization temperature and retrogradation rate of starch. Physical Properties In addition to predicting the rates of various chemical and enzymatic reactions, water activity effects the textural properties of foods. Foods with high aw have a texture that is described as moist, juicy, tender, and chewy (8). When the water activity of these products is lowered, undesirable texture attributes, such as hard, dry, stale, and tough are used. Foods with normally low aw have texture attributes described as crisp and crunchy, whereas higher aw levels may change the texture to soggy. Dry, cereal-based foods and starch-based snack products, such as crackers, potato chips, puffed corn curls, and popcorn, lose their sensory crispness with increasing water activity. The crispness intensity and overall hedonic texture of dry snack food products are a function of aw (9). Critical water activities are found when products become unacceptable from a sensory standpoint, falling into the aw range where amorphous to crystalline transformations occur in simple-sugar food systems and mobilization of soluble food constituents begins. Excessive and rapid drying or moisture reabsorption by glassy materials can cause undesirable consequences, such as product loss due to cracking and excessive breakage. Water activity is an important parameter in controlling water migration of multicomponent products. Some foods contain components at different water activity levels, such as cream-filled snack cakes or cereals with dried fruits. Moisture will migrate from a region of high aw to a region of lower aw; the rate of migration depends on many factors. Undesirable texture changes can result from moisture migration in multicomponent foods. For example, moisture migrating from the higher aw of dried fruit to the lower aw of cereal causes the fruit to become hard and dry, while the cereal becomes soggy (10). Water activity also is an important factor affecting the stability of powders and dehydrated products during storage. Controlling water activity in a powder product maintains proper product structure, texture, stability, density, and rehydration properties. Knowledge of the water activity of powders as a function of moisture content and temperature is essential during processing, handling, packaging, and storage to prevent the deleterious phenomena of caking, clumping, collapse, and stickiness. Caking is water activity, time- and temperature-dependent and is related to the collapse phenomena of the powder under gravitational force (11).

Ionic

Covalent

Solute & Capillary

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Fig. 1. Water ActivityStability Map (adapted from Labuza [1]). Table I. Water Activity and Growth of Microorganisms in Fooda Range of aw 1.000.95 Microorganisms Generally Inhibited by Lowest aw in This Range Pseudomonas, Escherichia, Proteus, Shigella, Klebsiella, Bacillus, Clostridium perfringens, some yeasts Salmonella, Vibrio parahaemolyticus, Clostridium botulinum, Serratia, Lactobacillus, Pediococcus, some molds and yeasts Many yeasts, Micrococcus Foods Generally in This Range Highly perishable (fresh) foods and canned fruits, vegetables, meat, fish, and milk; foods containing up to 40% (w/w) sucrose or 7% sodium chloride Some cheeses (cheddar, swiss, muenster, provolone); cured meats; some fruit juice concentrates; foods containing 55% (w/w) sucrose or 12% sodium chloride Fermented sausages; sponge cakes; dry cheeses; margarine; foods containing 65% (w/w) sucrose (saturated) or 15% sodium chloride Most fruit juice concentrates; sweetened condensed milk; flour; rice; pulses containing 1517% moisture Jam; marmalade Rolled oats containing 10% moisture; fudge; marshmallows; jelly; some dried fruits; nuts Dried fruits containing 1520% moisture; honey Pasta containing 12% moisture; spices containing 10% moisture Whole egg powder containing 5% moisture Cookies, crackers, bread crusts, etc. containing 35% moisture Whole milk powder containing 23% moisture; dried vegetables containing 5% moisture; corn flakes containing 5% moisture

0.950.91

0.910.87

0.870.80 0.800.75 0.750.65 0.650.60 0.50 0.40 0.30 0.20

Most molds, Staphylococcus aureus, most Saccharomyces (bailii) spp., Debaryomyces Most halophilic bacteria, mycotoxigenic aspergilli Xerophilic molds, Saccharomyces bisporus Osmophilic yeasts, few molds No microbial proliferation No microbial proliferation No microbial proliferation No microbial proliferation

Adapted from Beuchat (4).

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Shelf Life and Packaging Water activity also determines the shelf life of products. Critical upper and lower water activity levels can be established with respect to microbial, texture, flavor, appearance, aroma, nutritional, and cooking qualities of food products. Rates of moisture exchange through the package and the rate of change in aw of the food toward a critical limit determines the shelf life of a product. Knowledge of the temperature, ambient relative humidity, and critical aw levels can aid in selection of a package with the correct barrier properties to optimize quality and shelf life. Government Regulations The U.S. FDAs Good Manufacturing Practice (GMP) regulations (12) incorporate water activity guidelines in defining food safety regulations. The purpose of GMP regulations is to detail the specific requirements and practices to be followed by the industry to ensure foods are produced under sanitary conditions and are pure, wholesome, and safe to eat (13). However, neither GMP regulations nor regulatory agency activities alone can guarantee a completely safe food supply (14). A science-based system, such as hazard analysis and critical control points (HACCP), can improve food safety and reduce the incidence of foodborne illnesses. HACCP programs are mandatory for some segments of the food industry. HACCP is based on the idea that food safety problems can be controlled or prevented by controlling the production process from beginning to end, rather than relying on detection of problems in the finished product. HACCP identifies where potential hazards may occur in the food production process and determines critical control points for preventing problems. For example, a target water activity must be established to prevent hazardous organisms from growing. By controlling major food risks, such as microbiological, chemical, and physical contaminants, the food industry can better ensure the safety of its products. Water Activity Measurements In the past, measuring the water activity of foodstuffs was a time-consuming and difficult process. Methods of determining water activity are detailed in the Official Methods of Analysis of AOAC International (15). New instrument technologies have vastly improved the speed, accuracy, and reliability of measurements. Reliable laboratory instrumentation is required to guarantee the safety of food products and enforce government regulations. Two types of water activity instruments are available commercially. One uses chilled-mirror dewpoint technology, whereas the other measures relative humidity with sensors that detect changes in electrical resistance or capacitance. Each has advantages and disadvantages and varies in accuracy, repeat-

ability, speed of measurement, stability of calibration, linearity, and convenience. Dew point is a primary measurement of vapor pressure that has been used for decades (16). Dew-point instruments are accurate, fast, simple to use, and precise. (1720). The aw measurement range of commercially available dew-point meters is 0.030 to 1.000, with a resolution of 0.001 and accuracy of 0.003. Measurement time is typically less than 5 min. The basic principle involved in dew-point determination of vapor pressure in air is that air may be cooled without changes in water content until the air saturates. The

dew-point temperature is the temperature at which the air reaches saturation. It is determined by measuring the temperature of a chilled mirror when condensation begins. The water activity of the sample is the ratio of the saturation vapor pressure at the dew-point temperature to the saturation vapor pressure at the product temperature. In an instrument (AquaLab) dew point, the sample is equilibrated within the headspace of a sealed chamber containing a mirror, optical sensor, internal fan, and infrared temperature sensor. At equilibrium, the relative humidity of the air in the chamber is the same as the water activity of the

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CEREAL FOODS WORLD / 9

sample. A thermoelectric cooler precisely controls the mirror temperature. An optical reflectance sensor detects the exact point at which condensation first appears. A beam of infrared light is directed onto the mirror and reflected back to a photodetector that detects the change in reflectance when condensation occurs on the mirror. A thermocouple attached to the mirror accurately measures the dew-point temperature. The internal fan circulates the air, which reduces vapor equilibrium time and controls the boundary layer conductance of the mirror surface (21). Additionally, an infrared thermometer measures the sample-surface temperature. Both the dew-point and sample temperatures are used to determine water activity. When measuring water activity, the dew-point temperature is repeatedly determined until vapor equilibrium is reached. Because the measurement is based on temperature determination, calibration is unnecessary, but a standard salt solution can be run to check the proper functioning of the instrument. If there is a problem, the mirror is easily accessible and can be cleaned in a few minutes. Other instruments for measuring aw use resistance or capacitance sensors to measure relative humidity. These sensors are made from a hygroscopic polymer and associated circuitry that produces a signal relative to the equilibrium relative humidity (ERH). Commercially available instruments measure the entire aw range with an accuracy of 0.015. Because these instruments relate an electrical signal to relative humidity, the sensor must be calibrated with a minimum of five known salt standards. The ERH is equal to the water activity of the sample only as long as the sample and sensor temperatures are the same. Capacitive sensors typically require 30 to 90 min to reach complete temperature and vapor equilibrium. Accurate measurements require good temperature control. The advantages of capacitance sensors include simple design and inexpensive implementation. Conclusion For many foods, water activity is an important property in food quality and safety. It predicts food safety and stability with respect to microbial growth, chemical and biochemical reaction rates, and physical properties. The need to measure water activity in foods is illustrated by the FDAs incorporation of the water activity principle

A. J. Fontana, Jr. Anthony J. Fontana, Jr., Ph.D., is an applications engineer at Decagon Devices, Inc. He provides scientific and technical customer support and makes presentations of products, technologies, techniques, and applications to customers. In addition, he assists in product/technology development and testing. Prior to his work at Decagon, he managed a quality-control laboratory for a large cheese, whey protein concentrated, alcohol, and animal feed mix manufacturer. Dr. Fontana received his B.Sc. degree in Biochemistry from University of California, Riverside, in 1985, and his Ph.D. degree in Agricultural and Environmental Chemistry from University of California, Davis, in 1994.

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