Methods used to analyze water activity in foods

Introduction

The water activity (aw) of a food is the ratio between the vapor pressure of the food itself, when
in a completely undisturbed balance with the surrounding air media, and the vapor pressure of
distilled water under identical conditions. A water activity of 0.80 means the vapor pressure is 80
percent of that of pure water. The water activity increases with temperature. The moisture
condition of a product can be measured as the equilibrium relative humidity (ERH) By
measuring water activity, it is possible to predict which microorganisms will be possible sources
of spoilage. In addition to influencing microbial spoilage, water activity can affect the activity of
enzymes and vitamins in foods.

The equipment suitable for the measurement of water activity can be the same as that used for

the measurement of relative humidity provided that the sensing element used can be made

captive or otherwise isolated with a sample of the product to be measured. A basic measuring

technique utilizes a sealed dish or container with the sensor mounted above the test sample. For

initial screening purposes, all FDA district laboratories are equipped with the Abbeon a w-Value

Analyzer (a hair hygrometer). Samples can be tested in duplicate. The instruments are used to set

up a reference chart with data obtained from checks of reliable humidity generators. Salt slushes

of known aw values such as sodium chloride, potassium nitrate, and potassium sulfate can be

used. These salts will give a range of water activity (at 25 C) from 0.758 to 0.969. The results of

this test are an approximation which should then be confirmed by measurement, using pressure

equilibrium techniques in which the sample is allowed to come to equilibrium with a reference

standard, such as a microcrystalline cellulose (MC).

Since water activity is the ratio of the water vapor pressure of the sample to the water vapor

pressure of pure water under the same conditions, it is also equal to the equilibrium relative
humidity, ERH (expressed in %), divided by 100.Different types of instruments are used to

measure and analyze water activity. Methods vary in accuracy, repeatability, speed of

measurement, stability in calibration, linearity, and convenience of use.

Gravimetric method. In the isopiestic method, one determines the water activity of foods from

the sorption isotherms of suitable materials. In the so-called Fett-Vos method, the water activity

of food is determined by means of dried reference materials (proteins, microcrystalline cellulose)

The dried reference material is equilibrated with the sample in an evacuated desiccator, and any

weight alteration in the reference substance is then recorded. The water activity in the sample is

calculated from the change in weight and the known sorption isotherms of the reference

substances(Leonard,2002).

Psychrometric method. Sharpe et al. (1991) outlined a psychrometric technique for foods. The

instrument is valuable for the measurement of aw in cheeses, meats, preserves, butter, and canned

vegetables. The principle of the method is to use a miniature hygrometer probe which contains

both ‘dry’ reference and a ‘wet’ sensor. The latter is exposed to the atmosphere above the food

sample after equilibration. The resulting temperature change is a very linear function.

Hygrometric methods. These include: Salt method). The method is based on the fact that dried

salt adhering to filter paper is dissolved if the humidity of the surrounding air has reached a point

equal to the saturation humidity of the salt; Thread hygrometers. This method is based on the

hygroscopicity of the polyamide thread, which reacts to an increase in moisture by elongating

noticeably; Capacitance or electric hygrometers, consist of two charged plates separated by a

hygroscopic polymer membrane. As the membrane adsorbs water, its ability to hold a charge

increases. The resulting capacitance change is approximately proportional to the water activity as

determined by a sensor calibrated against known saturated salt standards. The sensor gives a
signal relative to the ERH and thus the water activity (as ERH/100). Commercially available

instruments measure over the entire water activity range with an accuracy of ±0.015 aw.; and

Conductivity hygrometers. With conductivity hygrometers, the measurement of electric

impedance of a liquid hygroscopic substance is used for direct reading of the relative humidity or

water activity in foods. The liquid hygroscopic materials include salt solutions or mixtures of

various salt solutions, depending on the make. These sensors are thus also called electrolytic

cells. The principle on which these cells are based relies (with only minor variations between

individual makes) on a very precisely defined tiny quantity of the hygroscopic material

sandwiched between a pair of electrodes mounted on a support plate (John A,2008).

Thermometric technique. The freezing point of a food is closely linked in a physical/chemical

sense with the water activity of the product. All those processes in a product that reduce the

water activity also lower the freezing point of the food. The point at which foods begin to freeze

can be measured and from this the aw level at 25ºC can be calculated. With this instrument water

activity, particularly for meat products, can be determined thermometrically. The measuring

system includes an electronic indicator module with a microprocessor, a cylindrical sample

chamber and a Peltier-cooling box at a temperature of approximately 50ºC. The measuring

period for this cryoscopic aw test on meat products depends on the aw level(Sood.V,2005)

Chilled-Mirror Dewpoint System. As air is passed over a chilled surface whose temperature is

gradually reduced, the temperature at which the water vapor begins to condense on the surface is

the dewpoint temperature, which is directly related to the vapor pressure of the air. The system,

provided only by Decagon, consists of a sensor block containing a dewpoint sensor, an infrared

thermometer, and a fan. A sample is placed in a sample cup which is sealed against the sensor

block. The dewpoint sensor measures the dewpoint temperature of the air, and the infrared
thermometer measures the sample temperature. The relative humidity of the headspace is

calculated as the ratio of dewpoint temperature saturation vapor pressure to saturation vapor

pressure at the sample temperature. When the water activity of the sample and the relative

humidity of the air are in equilibrium, measurement of the headspace humidity gives the water

activity of the sample. Chilled-mirror instruments make accurate (±0.003 aw) measurements in

less than 5 min, without the need for calibration.

Decagon’s introduction in February 2009 of its AquaLab Series 4TE Duo conducts both analyses

of water content and water activity in one instrument to save time and labor. The instrument uses

a chilled mirror to determine the water activity. Once the moisture sorption isotherm model for a

particular product is loaded into the instrument, it converts water activity into moisture content

and shows both aw and moisture content on the screen. The user of the instrument can select from

a library of isotherm models. Since the moisture sorption isotherm is complex and unique to each

product type, it must be determined experimentally by measuring water content at several water

activity values. Decagon offers a separate instrument, the AquaSorp, that can rapidly generate

isotherms, which can subsequently be loaded into the AquaLab Duo.

Water Activity Software Aids in Formulation Adria Development has created a computer

program that calculates water activity as a function of the composition of a product. AwDesigner

is said to determine water activity with the same precision as classical measurement methods and

predict the shelf life of new food products. It features a database of 160 ingredients—such as

starches, protein concentrates, fibers, gums, flours, fat, egg products, spices, meat, cereals, fruits,

and vegetables and 70 food additives, including preservatives, antioxidants, emulsifiers,

stabilizers, and gelling agents. The software includes mathematical models for calculating the

water activity of any formulation on the basis of the hygroscopic properties of the liquid and
solid phases that constitute the food. The calculations are based on published models-

Guggenheim–Anderson–de Boer (GAB) and Ferro-Fontan for the solid phase and Teng and Roa

for the liquid phase.

In determining the ERH (aw) several hours are required for the water vapor (relative humidity)

to reach equilibrium in the headspace above the food in the closed container. Therefore, the

formulation of the product to give the required aw must be predetermined and very accurately

compounded at the time of packing. It is necessary for the analyst to ensure that the temperature

of the supernatant air above the sample be closely controlled, as even a slight difference in

temperature in this area can result in a significant change in water activity reading. Stoloff (1978)

stated that at 25 C, a 0.1 C difference between the solid or liquid sample and the supernatant air

will result in an approximate 0.005 difference in water activity measurement.

All current instruments are affected by volatiles in one way or another. An additional challenge

is to develop a way to measure water activity online. Water activity can be measured at line but

not online, with the exception of some near-infrared systems but the challenge is to get

repeatable results.

Effects of water activity on food safety and stability

Introduction

Food should be stable and must be safe. These requirements mean that the products must not

endanger the health of the consumer with micro-organisms or their toxins, or deteriorate owing

to enzymic or microbial activity, at any stage from production through storage and retail to

consumption. For food, there are several factors that have a bearing upon any assessment of
microbiological stability, and thus upon the shelf life and safety of a product. Water activity aw

is a particularly important parameter for risk analysis as defined by the HACCP concept. Water

is essential for the growth and metabolic activity of micro-organisms. But not all of the water

present in food is in fact available for the biological activity of microorganisms or for other

chemical and enzyme reactions. Most foods have a water activity above 0.95 and that will

provide sufficient moisture to support the growth of bacteria, yeasts, and mold. The amount of

available moisture can be reduced to a point which will inhibit the growth of the organisms.

Water activity (aw) is a critical factor in determining quality and safety of foods. It affects shelf

life, safety, texture, flavor, and smell. The lowest aw at which the vast majority of food spoilage

bacteria will grow is about 0.90. Staphylococcus aureus under anaerobic conditions is inhibited

at an aw of 0.91, but aerobically a level is 0.86. The aw for mold and yeast growth is about 0.61

with the lower limit for growth of mycotoxigenic molds at 0.78 aw (Labuza,2007).

Water activity is the most important parameter of water in terms of food safety. Much of the

water in food is bound water, i.e. bound to ions as water of hydration, or bound to surfaces of

large molecule or cell structures. This water is not free to support microbial growth, or to

participate in or support chemical or enzyme reactions and spoilage processes. The total amount

of bound water in a food has no relation to food stability. The free or available water in a food

supports microbial growth, and participates in and supports chemical and enzymatic reactions

and spoilage processes. It is this amount of free water which is called water activity, aw, and it is

more important for food stability, chemical and microbial, than total water

content(Norman,2006).
Micro-organisms, like people, contain over 70 per cent water. A very important function of water

is maintaining osmotic pressure within the cell of the micro-organism and transporting nutrients.

This transport mechanism works principally because the necessary osmotic forces required for

osmosis between the inside of the cell and its surroundings are present. In this environment, the

endogenous and exogenous enzymes produced by the micro-organisms can play their role in the

microbial metabolism. By means of exogenous enzymes, larger molecules, which may not pass

through the cell membrane of the micro-organism, may be split up into smaller fragments, which

can then diffuse inside the cell through the osmotic barriers, aided by active transport

mechanisms(Beuchat,2004). Once here, the fragments are then either further oxidized directly by

endogenous enzymes or prepared for oxidation in several stages. If this ordered, highly

complicated cooperation between different enzyme systems in the living cell is disturbed, for

example by a reduction in the water activity, the reproduction, metabolic activity, resistance and

survival of the micro-organisms in the food are affected.

According to Samuel A. many traditional food preservation processes, such as salting, sugaring,

drying and freezing, alter the concentration of the particles dissolved in the water of the product

and thus its aw level. The transport of nutrients into the cell interior of the micro-organism is

affected by the reduction in water activity, since the osmotic pressure in the cell or its water

activity can be changed and adapted to environmental conditions only within a limited individual

range. The result is retarded growth of the micro-organism, or its death, thus producing a

stabilising or preserving effect on the food.

Micro-organisms occurring in food are frequently responsible for spoilage, and under certain

conditions also for food-induced infections or food poisoning. They may, however, be desirable,

for example to preserve and add flavour to meat products (raw sausage and raw ham) or to dairy
products by fermentation. All these desirable and undesirable microbial activities take place only

if the water activity of the product permits multiplication of the appropriate micro-organisms.

The water activity of food influences the toxin-forming ability of micro-organisms as well as

their growth. Water activity influences deteriorative chemical reaction rates because water acts

as a solvent, can be a reactant itself, or can change the mobility of reactants through viscosity.

One or a combination of any of these factors can lead to faster deterioration and a shortened

product shelf life. Non-enzymic browning reactions increase with increasing aw to a maximum

at 0.6 to 0.7aw. Lipid oxidation has a minimum at about 0.2 to 0.3aw. Moisture migration is a

major cause of deteriorative physical changes and texture loss in food. Water activity is a

function of temperature, thus shipping and storage temperature changes water activities effect on

the microbial, chemical and physical properties which affect safety and stability of foods.

Changes in water activity by absorption of water when a product is exposed to a high humidity

environment or loss of water when placed in a low humidity environment brings about

undesirable changes in products and shortens shelf life. These changes can be physical, such as

loss of crispness in dry products, caking and clumping of powders, or moist products losing

water to become tough and chewy. Other undesirable changes are acceleration of chemical

deterioration, or potential for microbial growth which renders food unsafe for human

consumption.

Conclusion

Water activity in food has been controlled by drying, addition of sugar or salt and freezing.

These methods prevent spoilage and maintain food quality. Water activity is the ratio of the
partial vapor pressure of water in equilibrium with a food to the partial saturation vapor pressure

of water vapor in air at the same temperature. This is equal to the relative humidity of air in

equilibrium with the food. The water activity of a food describes the energy state of water in the

food, and hence its potential to act as a solvent and participate in chemical/biochemical reactions

and growth of microorganisms. It is an important property that is used to predict the stability and

safety of food with respect to microbial growth, rates of deteriorative reactions and

chemical/physical properties. Monitoring water activity is a critical control point for many

manufacturers and should be incorporated into many other food safety programs. The number

one priority is protecting the consumer.

References
Beuchat, L.R. Microbial stability as affected by water activity. Cereal Foods World, 26(7), pp.

345-349. 2004.

M. Karel, O. Fennema and D. Lund. Physical Principals of Food Preservation. Marcel Dekker

Publ. 2004.

Norman N. Potter. Food Science. The AVI Publishing Co., Inc. 2006.

John A. Troller. Statistical Analysis of aw Measurements. Journal of Food Science, Vol. 42,

2008

Samuel A. Matz. The Relation of Microbial Spoilage To Water Activity of Foods. The AVI

Publishing Co.

Leonard Stoloff. Calibration of Water Activity Measuring Instruments and Devices:

Collaborative Study. J. Assoc. Off. Anal. Chem., VoL. 61, No. 5, 1991.

Labuza, T.P. Properties of water as related to the keeping quality of foods. Proceedings of the

Third International Congress of Food Science & Technology. Washington, DC., pp. 618-635.

2007

María S. Tapia Stella M. Alzamora , Effects of Water Activity (aw) on Microbial Stability: As a

Hurdle in Food Preservation.2017

Sood, V. C. and Heldman, D. R. (2005) ‘Analysis of a vapor pressure manometer for

measurement of water activity in nonfat dry milk’. Journal of Food Science, 39, 1011–1013.

Sharpe, A.N., Diotte, M.P. and Dudas, I. (1991) ‘Water activity tester suited to compliance and

high aw work’. Journal of Food Protection, 54, 277–282.

Jorge Cir