Water content, water activity, water structure

and the stability of foodstus

Mohamed Mathlouthi
*
Laboratoire de Chimie Physique Industrielle, Facult e des Sciences, Universit e de Reims Champagne-Ardenne, B.P. 103951687 Reims C edex 2, France
Received 11 December 2000; received in revised form 7 March 2001; accepted 8 March 2001
Abstract
Determination of water content, whatever the accuracy of the analytical method, is not suciently informative in relation to the
stability of the investigated food product. Water activity (a
w
) brings a supplement of information as it accounts for the availability
of water for degradation reactions.
The understanding of why certain products are more stable than others at the same a
w
needs an elucidation of water structure. Of
particular importance are the interactions (hydrophilic, hydrophobic) between water and the components of the foodstu and the
eect of the soluble molecules of the food on the hydrogen bonding in solvent water.
Studying water in foods should start with an anlytical determination of water content for commercial and legal reasons which are
evident. This has to be completed with the measurement of the thermodynamic activity of water in the food. Such a parameter (a
w
)
should hold an important place in the identication of the food product, especially as regards its shelf life. A further step in unveiling
the behaviour of water in foods consists in determining water molecules in the molecules in the studied food matrix.
The tripartite (analytical, thermodynamical and structural) approach to water in foods will be examined based on examples of
sugars and sugar rich products. 2001 Elsevier Science Ltd. All rights reserved.
1. Introduction
Water is omnipresent in foodstus and the surround-
ing atmosphere. Determination of water content is one of
the most frequent analysis in the laboratory of a food
industry. However, depending on the method of analy-
sis, it is not the same type of moisture content, which
is measured. Even the term ``moisture'' itself is ques-
tionable as this might include other liquids than water,
wetting the product (Isengard, 1995). The most common
method of water analysis usually accepted at a commer-
cial level is the desiccation method. This method is based
on the mass loss after drying of the sample. However,
part of mass loss might originate from the volatility of
other gases than water. Not only the desiccation or ``oven
drying'' is criticisable, but also all methods of determi-
nation of water contents have their drawbacks.
The sole value of ``water content'' in a food is not
inform about the nature of water, if it is ``bound'' or
``free'', ``inherent'' or ``occluded'', etc. The knowledge of
each of these fractions is important as it helps in un-
derstanding the process which is at the origin of each
fraction.
Beside measuring water content in the foodstu,
many laboratories are now equipped with devices which
allow determination of water activity (a
w
). However,
depending on the technique of water activity measure-
ment, the result may be dierent. It is necessary for a
slow equilibrium between the product and air sur-
rounding it that this equilibrium is reached. The ob-
taining of equilibrium is asymptotic. One has to inform
about the time needed to reach such an equilibrium.
Rapid measurement of a
w
using the dew point technique
only gives the surface equilibrium relative humidity
(ERH) of the product, which may not be sucient for
shelf-life prediction for example. To account for the
behaviour of a food product in the whole range of rel-
ative humidities to which it may be submitted during
storage, there is a need of establishing the water vapour
sorption isotherm, preferentially at storage temperature.
The shape of sorption isotherm may change de-
pending on the type of product and its anity for water.
Brunauer, Emmett, and Teller (1938) have described ve
Food Control 12 (2001) 409417
www.elsevier.com/locate/foodcont
*
Tel.: +33-326-913-239; fax: +33-326-91-3304.
E-mail address: mohamed.mathlouthi@univ-reims.fr (M. Math-
louthi).
0956-7135/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 5 6 - 7 1 3 5 ( 0 1 ) 0 0 0 3 2 - 9
types of water vapour sorption isotherms. Soluble foods
like sugar adopt an asymptotic shape of isotherm when
relative humidity tends towards 100%, and heteroge-
neous complex foods show a sigmoid curve. Analysis of
the shape of sorption isotherms shows that they may be
divided into three zones, respectively, corresponding to
monolayer strongly bound water, linear region of less
rigidly and capillary adsorbed water and the third region
of solvent or free water.
This description of the three species of water is a
rough accounting of the dierences in the structure of
water. Indeed, equilibrium of hydration of a food gen-
erally described by water activity (a
w
) depends on the
structure of food components, their eect on the solvent
(water) and other properties like the surface activity of
the product. Direct analysis of the structure of water in a
food system is dicult to achieve. Utmost, one can have
an insight into ``free'' and ``bound'' water from NMR or
other techniques like thermal analysis of frozen systems.
Amid the water properties that may be used for the
elucidation of its structure, the behaviour as a solvent
and the interactions with dierent classes of molecules
are of great importance.
2. Water content
Determination of water content in foodstus can be
performed using either direct or indirect methods. Direct
determinations may be based on some physical separa-
tion techniques like distillation, drying or chemical re-
actions producing gases like H
2
or C
2
H
2
which are
measured using specic techniques.
Indirect determinations rely on the spectroscopic
properties of water molecules. It is the case for NMR,
infrared and Raman spectroscopy which are non-de-
structive techniques, as well as microwave spectroscopy
or microwave resonator methods. Some properties of
the foodstus especially sugar solutions and fruit juices
allow obtaining of the dry substance (concentration) in
the medium. These properties are either optical (refrac-
tometry, polarimetry), gravimetric (density) or electrical
(conductivity) and allow indirect determination of water
content (as a dierence).
A rapid survey of these methods is given together
with the limits and disadvantages they might have. Their
suitability to the prediction of food product stability is
also reported.
2.1. Direct determination
2.1.1. Physical separation
Oven drying for a standardised period and a con-
ventional temperature (3 h at 105C for sugar) is very
often the legal method of determination of water con-
tent. The period of drying is specied for each type of
product. Dierent sources of errors may be found in
oven drying. These are, for example, the incomplete
removal of water, the loss of other volatiles than water
during the drying period, the formation of a crust at the
surface of the product which slows down the escape of
water, the decomposition of the product and Maillard
reaction which produces water.
Vacuum-oven drying takes place at lower tempera-
tures (~70C) for longer periods (~6 h). Such conditions
may be less destructive for heat sensitive samples.
Nevertheless, duration of drying may not be sucient to
allow the food to come to steady state. Size of particles
inuences both oven and vacuum-oven drying.
Solvent extraction may be used to extract water form
food with an organic solvent prior to its analysis using a
chemical titration.
Distillation which cannot be used for the analysis of
traces of water has a relatively long duration (P1 h)
(Isengard, 1995).
2.1.2. Chemical reactions
Dierent quantitative chemical reactions, which pro-
duce gas, exist and can be used to quantify water content
provided that the released gas is accurately analysed.
Amid these reactions, we nd
H
2
OCaH
2
CaOH
2
O (1)
H
2
OCaC
2
CaOC
2
H
2
(2)
Reaction (2) is still used in sugar lump workshops to
have a rapid (1020 min) tool of controlling the rate of
moisturising the sugar prior to pressing and drying the
cubes. Volume of C
2
H
2
, which is directly linked to water
content, might change as a function of temperature in
the workshop.
Karl Fischer titration: Karl Fischer initiated this
method in 1935, who introduced a reagent specic of
water which contains pyridine, methanol, sulphur di-
oxide and iodine. Later, it was shown (Verhoef & Ba-
rendrecht, 1976) that pyridine is not necessary and could
be replaced by other bases with higher basicity whereas
methanol which takes part in the reaction cannot be
replaced by other alcohols (Isengard, 1995).
Using imidazole (Z) as a base, we have a two-step
reaction at the basis of water titration
CH
3
OHSO
2
Z ZH

CH
3
OSO

2
ZH

CH
3
OSO

2
I
2
H
2
O2Z
3ZH

CH
3
OSO

3
2I

The titrating reagent is I

2
, which reacts stoichiomet-
rically with water. The rst excess of I
2
indicates the
end-point of reaction. Indication of end-point is ob-
tained through an abrupt drop of voltage due to the
presence of the redox couple I
2
=I

at the polarised
platinum electrodes. Karl Fischer titration proves to be
the most accurate method, which can be used for all
410 M. Mathlouthi / Food Control 12 (2001) 409417
values of water content from traces to high levels. This
method is now computerised and is more and more used
especially as sugars contain only traces of water.
2.1.3. Chromatography
Gas chromatography has been applied to the deter-
mination of water content in freeze-dried vaccines
(Bervelt, 1975). However, there is a need that water is
extracted by organic solvent prior to analysis and that
the sample is homogeneous. Extraction solvent should
have a high anity for water and be protected from the
surrounding atmosphere humidity. Using methanol or
DMF together with molecular sieves as in Karl Fischer
titration, proves to be an ecient method of extraction.
Generally, Porapaq-Q is used to ll the column. This
method is relatively rapid providing that the solvent or
other impurities do not have peaks that obscure the
peak of water.
2.1.4. Spectroscopy
Interaction of the water molecule with electromag-
netic radiation may be used in the analysis of water
content. The fact that hydrogen atoms in water have
nuclei which possess magnetic properties allowing them
to behave as small bar magnets is exploited in proton
NMR for the determination of water in foods (Troller &
Christian, 1978).
NMR spectroscopy is informative on hydrogen at-
oms. These are more easily detected in a liquid envi-
ronment. So that this technique is more adapted to
distinguish between free water and bound water (crys-
tallisation water for example) than the accurate deter-
mination of water content. Moreover, there is a need of
obtaining precise calibration specic of the analysed
product based on a good reference method.
Near infrared (NIR) absorption of water occurs at
dierent wavelengths (1950, 1450 and 977 nm). The ra-
tios of the intensities of the bands at 1950 and 1450 nm
are used as a measure of water content (Vornhof &
Thomas, 1970). It is also possible to extract water from
the food with a solvent (methanol, dimethylformamide)
prior to analysis by NIR spectroscopy.
Computerised NIR spectrometers are used in dier-
ent food industries for the determination of water con-
tent and other food constituents. This method requires a
specic calibration for the food analysed and the use of
statistical methods of exploitation of results which are
included in the software. The colour, particle size,
thickness and texture of the product inuence results.
The reectance technique allows detection of surface
water and might not be representative of the whole
product if it is not homogeneous.
Microwave spectroscopy uses the dipolar character of
water molecules. The shift in wavelength and the at-
tenuation of the amplitude of the waves when a sample
is placed between the emitter and receiver of microwaves
are used to determine the amount of water content (Is-
engard, 1995). Parameters such as water concentration,
density and thickness of the analysed sample may have
an eect on the result. Mobile water can be measured
more easily than bound or crystallisation water. A cal-
ibration is needed. The method may be used for on-line
measurements provided that the thickness of sample is
known.
Another application of microwaves to the determi-
nation of water in foods is that of the resonator. If a
sample containing water is put in the resonator cham-
ber, the resonance frequency of microwaves shifts under
the eect of water as well as the height of the resonance
peak. Again a specic calibration is needed.
2.1.5. Physical properties related to water content
Refractometers are used to determine the percentage
of sugar in sugar syrups or fruit juices. By dierence to
100, the water content is deduced. Polarimetry is also
used for pure sugar solutions or technical sugar solu-
tions after defecation and ltration. These optical
methods only determine optically active substances and
the water content is only determined by dierence. This
might be sucient for a rapid analysis of syrups.
Thermal analysis using dierential thermal analysis
(DTA) or dierential scanning calorimetry (DSC) may
be used during the heating of a frozen sample to deter-
mine freezable water, which is approximately the frac-
tion of water, considered as mobile or ``free''. Such
techniques are also informative on the glassy state of
water in foodstus, which might help in the interpreta-
tion of the behaviour of the product during drying.
3. Water activity and sorption isotherms
Most of the methods used for the determination of
water activity or ERH of foods were originally set for
the measurement of relative humidity in atmospheric air
by the meteorologists (Troller & Christian, 1978). When
water activity (a
w
) is measured it is generally required to
know if the product has reached the critical zone where
spoilage reactions may occur or not. That is why accu-
racy within 0.01a
w
unit is sucient for most food-related
applications.
Water activity is dened as the ratio of partial pres-
sure of water vapour in the product (p) to that in pres-
ence of pure water (p
o
):
a
w
=
p
p
o
:
If there was no dierence in the interaction between
water and water on the one hand and water and solute
on the other, the determination of water activity would
have been easy and its expression
a
w
=
n
2
n
1
n
2
= X
w
M. Mathlouthi / Food Control 12 (2001) 409417 411
directly obtained from the mole fraction X
w
of water
molecules (n
2
) to total molecules in the solutions. For
real solutions A
w
= c X
w
, where c is an activity coe-
cient. The higher the modication of water binding by
the solute, the more c coecient is dierent from 1.
3.1. Manometry
As water vapour pressure is given in tables for dif-
ferent temperatures, a direct measurement of water va-
pour pressure in the food should give the best direct tool
of determination of a
w
. To achieve this measurement
there is a need of establishing vacuum and working at
temperatures as low as )80C. Working at zero pressure
in one side of the oil manometer with the freeze trap of
moisture and leaving the sample on the other side release
its vapour permits accurate measurement of a
w
. This
method needs uniform accurate temperature measure-
ment and the device is extremely fragile (Troller &
Christian, 1978).
3.2. Electric hygrometer
The sample is placed in a tight measuring chamber at
a controlled stable temperature. During equilibration
the sample releases humidity and the same relative hu-
midity at the level of the electrical sensor and in the
sample is observed. The sensing element may be either a
conducting polymer or an electrolytic element like sat-
urated LiCl solution. Another type of electric hygrom-
eter uses the measurement of electrical conductivity or
capacitance of a hygroscopic substance like LiCl crystal
or the anodised surface of an aluminium rod (Troller &
Christian, 1978). Filters that adsorb contaminants are
often needed. The sensors need frequent calibration with
saturated salt solutions. Except in the extremes of the
water activity range (below 0.15 or above 0.95), the
accuracy of the electric hygrometer is satisfactory.
Among the drawbacks of this type of a
w
-meter are the
hysteresis observed and the sensitivity of sensor to high
relative humidities (near saturation).
3.3. Dew point
Dew point measurement is also used to determine a
w
.
The temperature at which saturation of water is ob-
served and the beginning of condensation which is ob-
tained at the cooled surface of a mirror is related to
vapour pressure and consequently to a
w
. This is well
known from the psychrometric chart of humid air.
Photodetection of the condensation on the cooled (Pel-
tier eect) mirror together with the precise measurement
of mirror allows deducing of relative humidity in the cell
where the sample of food was disposed. However, al-
though this type of measurement can be rapid and
precise, it only accounts for surface a
w
. The surface of
the mirror should be clean and non-contaminated and
the amount of condensed water negligible if it is desired
to have the measured relative humidity equal to ERH of
the food.
3.4. Other methods of measurement of relative humidity
Other methods of measurement of relative humidity
may be used to determine a
w
. It is the case for the wet
bulb-dry bulb thermometric technique, the hair hy-
grometer, the freezing point depression or the aptitude
of certain chemical compounds to change colour at a
given relative humidity. These methods may be used to
give an approximate value of a
w
during the storage of a
food product.
3.5. Water vapour sorption isotherms
3.5.1. General aspect and meaning
A water vapour sorption isotherm represents the
variation of water content as a function of water activity
at a given temperature. The general aspect of a sorption
isotherm usually observed for a food product is sigmod
(Fig. 1).
Fig. 1. Three regions of water vapour sorption curve and the BET
method of determination of monolayer water.
412 M. Mathlouthi / Food Control 12 (2001) 409417
This curve is established using a microclimate method
or an electrical hygrometer equipped with the sorption
accessory. In the microclimate method a small amount
of sample is disposed in a cupel as a thin layer. The cupel
is placed in a gas-tight jar where relative humidity is
xed with saturated salt solutions (Table 1).
Evolution of product water content, which should be
determined prior to submitting the samples to water
activity equilibration, is followed by weighing. When
equilibrium (constant mass) is reached, by sorption or
desorption, the water content at equilibrium is repre-
sented as a function of ERH or water activity
(a
w
= ERH=100). The water vapour sorption curve
obtained is composed of three regions A, B and C.
Region A corresponds to hydration monolayer where
water molecules are bonded to the product by strong
H-bonds. The amount of monolayer water may be
determined using BET (Brunauer, Emmett and Teller)
isotherm method (Brunauer et al., 1938) (Fig. 1). The
BET isotherm is expressed by
a
w
(1 a
w
)m
=
1
m
o
c

c 1
m
o
c

a
w
;
where a
w
is the water activity; m the water content (dry
basis); m
o
the water content in the monolayer and c is
the constant related to adsorption heat.
This relation is applicable for a
w
60:55.
From a=(1 a)m = f (a
w
), it is possible to determine
graphically
m
o
=
1
ordonate at the origin slope
and
c =
1
(ordonate at the origin m
o
)
= eQs=RT
with Q
s
the heat capacity of the monolayer.
Region B corresponds to the linear part of sorption
isotherm (Fig. 1). Water is adsorbed as multilayers of
molecules of hydrogen bonded to the monolayer, or
entrapped in the food by capillarity, Van der Waals
forces, etc.
Region C is that of the so-called ``free'' or solvent
water. Water molecules in this region are much less
strongly bound than in regions A and B. This fraction of
water is available for mould growth or dissolving of
soluble solutes. Sorption of water vapour by solid
foodstus shows very often a hysteresis phenomenon.
Adsorption and desorption curves are not superposed
(Fig. 2).
The origin of hysteresis is linked to the type and
strength of the bonds between water and product. It is
well known that lling and emptying of capillaries in
the product does not follow the same kinetics. This is
one reason for the dierence between adsorption and
desorption isotherms. Another reason is the change in
the structure of some food constituents (starch for
example) when they are submitted to various a
w
.
Hysteresis is generally observed at water contents
above monolayer.
Hysteresis of sorption isotherms has some conse-
quences as regards chemical and microbial stability
of food products. The fact that water content is higher
for desorption than for adsorption at the same a
w
leads to degradations such as the loss in vitamin C for
a model food system prepared by desorption in
the range of a
w
from 0.32 to 0.93 (Lee & Labuza,
1975).
3.5.2. Application of sorption isotherms
Sorption isotherms are important for more than one
reason. From the point of view of thermodynamics, they
are informative on sorption and desorption enthalpies
and the type of binding of water to dry matter. On a
structural level, they can help in understanding the role
of particle size, amorphous state or specic area in water
vapour sorption. Concerning the technological aspect,
water vapour sorption isotherms are useful in the
prediction of shelf-life, the control of drying and the
Table 1
Saturated salt solution a
w
LiCIH
2
O 0.12
CH
3
COOK 0.23
MgCl
2
6H
2
O 0.33
K
2
CO
3
0.44
Mg(NO
3
)
2
6H
2
O 0.52
NaCl 0.75
(NH
4
)
2
SO
4
0.79
CdCl
2
0.82
Li
2
SO
4
0.85
K
2
CrO
4
0.88
KNO
3
0.94
K
2
SO
4
0.97
Na
2
HPO
4
0.98
Fig. 2. Hysteresis of water vapour sorption isotherms.
M. Mathlouthi / Food Control 12 (2001) 409417 413
prevention of such accidents as caking and sticking of
food powders.
3.5.2.1. Storage stability sugar. If sugar for example, if
crystalline is stable when a
w
is maintained below 0.83
(Fig. 3). Stability can be reached easily at ordinary
temperature and relative humidity for pure sucrose well
crystallised. If some impurities are remaining at the
surface in the thin lm of saturated syrup surrounding
the crystals, the behaviour of sugar towards water va-
pour may change. As a general rule, impurities in sugar
syrup increase sugar solubility, which leads to a lowered
water activity of saturated solution. This means that
problems such as caking or stickiness may occur at
relative humidities below 80%.
The same type of instability occurs when the size of
crystals is small or when amorphous sugar obtained by
the breakage of crystals or by a rapid drying at high
temperature is present at the surface of sugar crystals.
Recrystallisation of amorphous sugar may occur at
relative humidities as low as 38% at 20C (Fig. 4) with
release of water which dissolves more sugar initiating a
caking process. If the impurities at the surface of sucrose
crystals involve other sugars more hygroscopic like
glucose or fructose, then the instability of sugar is ob-
served at lower relative humidities.
3.5.2.2. Shelf-life and water activity of intermediate
moisture foods. Water availability for microbial spoil-
age in intermediate moisture foods (IMF) can be mini-
mised through formulation. For sponge cake, taken as
an example of IMF, usually water activity is around
90%. Adding water activity depressors to the formula of
the cake combined with modied atmosphere packaging
(MAP) (less than 1% of O
2
) proves to be an ecient
method for extending the shelf-life from few days to
several months.
Change in water availability during storage of
sponge cake may be manifested by a hysteresis between
adsorption and desorption isotherms. To minimise
sorption hysteresis and depress signicantly (from 0.90
to 0.84) the value of a
w
of sponge cake, the addition of
0.51% of soya protein was found ecient (Guinot,
1988). Moreover, eciency of water retention is in-
creased if additive is added to ``creaming'' which is
treated thermally by heating at 45C for 10 min. Such a
treatment allows the globular structure of protein to
unfold and sites of xation of water molecules by H-
bonds to become available. Combining this formula-
tion modication with MAP (50%CO
2
50%N
2
) and
storing the product at 4C allows the increase of shelf-
life of sponge cake up to 10 weeks without microbial
spoilage.
Water activity depressors prove to be useful in in-
creasing the stability of baked goods. If sucrose is taken
as a reference standard with humectancy (a
w
depressor
ability) equal to 1, then it may be observed that dierent
ingredients used to prepare cakes might be more or less
good humectants (Table 2).
Fig. 3. Water vapour sorption isotherm of crystalline sugar.
Fig. 4. Water intake by amorphous sugar.
Table 2
Comparison of humectancies of cake ingredients with sugar taken as
reference standard (humectancy =1)
Product Humectancy
Flour butter 0.2
Fat, egg 0
Skin milk powder 1.2
Raisins 0.9
Leavening powder 3
Salt 11
Tartaric and citric acids 3
Glucose syrup 42 DE (DS) 0.7
Glucose syrup 64 DE (DS) 0.9
Glucose, fructose, invert 1.4
Sorbitol 2
Glycerol 4
414 M. Mathlouthi / Food Control 12 (2001) 409417
However, glycerol although a good water activity
depressor might not be the ideal ingredient to protect
against bacterial growth. Water although retained
around glycerol molecules is mobile enough to allow
the growth of bacteria (Sperber, 1983). It is also the
case for fructose, which is also known to have much
mobile hydration water around it than sucrose or
glucose.
4. Water structure
Most of the reactions occurring during the storage
of a foodstu, like lipid oxidation, enzyme degrada-
tion, Maillard reaction may nd an interpretation re-
lated to the structure of water. Likewise the specic
interactions of the dry substance with water, namely
hydrophilic or hydrophobic interactions can be helpful
to understand the behaviour of the product towards
water vapour during its preservation. A brief recall of
the structure of pure liquid water will be reported be-
fore the description of solutesolvent interactions in
foods and their consequences on the stability of food
products.
4.1. Liquid water structure
The chemical structure of H
2
O, where an atom of
oxygen occupies the centre of a regular tetrahedron,
two vertices of which are the H atoms and the two
others the lone pairs of electrons of the oxygen atom, is
at the origin of its 3D structure. Indeed, such a con-
guration allows each water molecule to be associated
to four molecules by H-bonds. Moreover, hydrogen
bonds are sensitive to charge transfer from donors to
acceptors in a sequence which produces an eect called
``cooperativity'' (Frank, 1974). Other liquids like alco-
hols form chains of H-bonds because they have only
one hydroxyl group whereas water forms tetrahedral
clusters.
Water structure was one of the most studied subjects
these last years using either computer models or exper-
imental spectroscopic techniques. However, no theory
or conclusions drawn from experimental results can
account for its particular physical properties. Computer
models for water structure generally describe this liquid
as a continuous network of H-bonds randomly ar-
ranged. These models have two disadvantages: the lack
of details and a static character. Experimental tech-
niques such as neutron scattering, FTIR and Raman
spectroscopy were used to investigate structure and dy-
namics of the hydrogen bonding in liquid water. De-
composition of the experimental Raman band in four
components assigned to four species of clusters with H-
bonds diering in strength and number was proposed by
Luu, Luu, Rull, and Sopron (1982). Such a model may
be adopted as a reference for comparative studies of the
eect of solutes on water structure.
4.2. Hydrophilic interactions
Cations of interest in the food industry like
Na

; Ca
2
or Mg
2
are known to immobilise several
layers of hydration water. Generally such ions are
known to have three layers of water around them. A
rst layer strongly bound to the ion, a second layer of
perturbed water because it is submitted to the attrac-
tion due to electrical eld of the ion on the one hand
and to the ``cooperativity'' of H-bonds with water
molecules of the third layer where water is less inu-
enced by the ion.
Beside this type of attraction of water molecules
around a hydrophilic solute, the hydration of small
non-electrolytes and biopolymers is generally consid-
ered as hydrophilic. Small hydrophilic molecules like
sugars have a sphere of hydration characterised by a
number of hydration (ve for sucrose) and a ``structure
maker'' eect as they have a long-range eect of ori-
entation of bulk water molecules. The hydration of
food polymers is sensitive to their conformations and
this can be measured by dierential scanning calori-
metry (Silvonen, Lindberg, Seppala, Evasti, & Hauta-
hoo, 1982). It is also important to take into account
the eect of the phase (gel, emulsion,) in which the
biomolecules are embedded, which may change their
conformation. In particular globular proteins may
change conformation as concentration is increased and
temperature raised to expose their hydrophobic back-
bone to water and establish intramolecular H-bonds.
Interactions of water with the hydrophobic surface of
folded proteins corresponds to the so-called hydro-
phobic hydration.
4.3. Hydrophobic interactions
Hydrophobic interactions are due to the hydration of
apolar groups like methyl groups. Interaction between
such a group and water is weaker than waterwater
hydrogen bonding, so that, when several water mole-
cules surround an apolar group, they do not have a
direct contact with the group and hence reinforce their
waterwater bonds. This layer of water is much less
mobile than bulk water. Its enthalpy is decreased and its
entropy is increased. Hydrophobicity of proteins may be
at the origin of the stability of emulsions. Processed
meat products may be considered as emulsions where
hydrophobic hydration of the proteins together with the
hydrophilicity of salt and glycerol tends to immobilise a
maximum of water and to increase the shelf-life (Lacroix
& Castaigne, 1984).
M. Mathlouthi / Food Control 12 (2001) 409417 415
Beside the structure of water near hydrophobic bio-
polymers, it is needed to know the type of organisation
of water molecules in the vicinity of solid interfaces to
interpret their sorptiondesorption behaviour, which
very often exhibits hysteresis phenomenon.
4.4. Interfacial water and sorption hysteresis
Physical properties of interfacial water seem to be
dierent from those of bulk water. Water molecules in
the vicinity of adsorption sites at the surface of a solid
are more rigidly organised. The kinetics of adsorptoin of
water by proteins at airwater interface is very slow
(Terminassian-Saraga, 1981), and protein denaturation
is found to depend on surface tension of the adsorbed
lm of water.
Water vapour sorption by foods is sensitive to surface
tension. This was demonstrated (Labuza & Rutman,
1968) by use of tensioactive agents in model systems.
Increasing the surfactant in the formula induces a de-
crease in water content. Surfactants also decrease the
hysteresis amplitude. Moistening by the tensioactive
agent reduces to 0 the dierences between contact angles
during sorption and desorption processes. Moreover, an
``ink bottle'' model for capillaries seems to be conve-
nient and supports the hypothesis of surface tension
decrease by the surfactant, which changes the mecha-
nism of capillary lling.
4.5. Water structure and food preservation
Extending the shelf-life of a food product consists in
preventing its degradation by biochemical reactions or
microbial growth. Prevention of degradation means
prevention of availability of water for degradation re-
actions (Mathlouthi, 1986). To achieve such an objec-
tive, it is necessary to reinforce the hydrogen bonding of
water and to reduce its mobility. Such a result may be
obtained through the formulation of the product and
the control of the type of hydration by establishing
water vapour sorption curves. It is also useful to know
the thermal history of the product (thermal treatment,
storage temperature) in order to interpret the change in
mobility of water.
For the inhibition of growth of micro-organisms, it is
needed to lower a
w
. However solutes like glycerol, al-
though good water activity depressors, may enter the
bacterial cell without causing an osmotic stress, so that
bacteria grow in presence of glycerol at low a
w
values. It
seems that viability of pathogen bacteria in foodstus is
controlled by osmotic pressure regulation with dierent
solutes (Sperber, 1983). So that retention of water by an
additive is not the sole parameter in formulation. It is
also needed to know the eect of solute on water mo-
bility.
5. Conclusion
The sole determination of water content, even using
accurate methods like Karl Fischer titration, is not
sucient to predict their shelf-life. Water activity proves
to be a good indicator of the preponderance of one or
another of the degradation reactions that might occur
during storage of foodstus. For example, lipid oxida-
tion occurs below a
w
= 0:30 and Maillard reaction ex-
hibits an optimum for a
w
= 0:65. To understand the
mechanisms of degradation reactions and why some
foods are stable whereas others are not stable at the
same a
w
, there is a need of knowledge of the nature and
concentration of the dierent components and of water
structure. Mobility of water and its availability for
biochemical reactions depend on the type of interaction
it might have with solutes.
Approaching water in foodstus, especially in view of
studying storage stability and shelf-life should rely on
three types of information: analytical determination of
water content, thermodynamical activity of water and
the unveiling of water structure in presence of the sol-
uble constituents of the foodstu.
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