LWT - Food Science and Technology 42 (2009) 1621–1628

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LWT - Food Science and Technology

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Reducing salt level in food: Part 2. Modelling salt diffusion in model cheese
systems with regards to their composition
Juliane Floury a, *, Olivier Rouaud b, Maëva Le Poullennec c, Marie-Hélène Famelart a
a
UMR 1253 – Science et Technologie du Lait et de l’Oeuf, INRA AGROCAMPUS OUEST, 65 rue de Saint-Brieuc, F-35042 Rennes cedex, France
b
UMR CNRS ENITIAA-GEPEA, rue de la Géraudière, BP 82225, 44322 Nantes Cedex 3, France
c
IUT de Chimie– rue du Clos Courtel, BP 90422 – 35704 Rennes cedex 7, France

a r t i c l e i n f o a b s t r a c t

Article history: In the first part of the paper (Floury, J., Camier, B. Rousseau, F., Lopez, C., Tissier, J. P., & Famelart, M. H.
Received 19 March 2008 (2009) Reducing salt level in food: Part 1. controlled manufacture of model cheese systems and their
Received in revised form structure-texture relationships. LWT – Food Science and Technology 49(10), 1611–1620), a model cheese
2 June 2009
matrix presenting different textural properties was developed in order to further study the factors
Accepted 3 June 2009
implied in the salt release in mouth during food chewing. The present work consists in physical and
modelling approaches to better understand the mass transfer phenomena occurring in the product
Keywords:
during its consumption in the mouth. Concentration profiles of several ionic species were measured
Model cheese
Ionic species during the release of salt from the different model matrices into artificial saliva. Apparent diffusion
Sodium chloride coefficients of the sodium chloride were determined by fitting the experimental data to the second Fick’s
Modelling law. Apparent diffusion coefficients were included between 2.81 and 3.43  1010 m2 s1 at 15  C and
Mass transfer 75% HR. D-value decreased strongly when the dry matter content decreased. Microstructure of the
matrices with the lower protein concentration was coarser and fluffier, facilitating the diffusion of the
solutes. The D-value increased with the pH at renneting, probably because of the chemical changes of
the structure of the casein micelles and significant differences in textural characteristics of cheeses. The
diffusion coefficient also significantly decreased with the initial salt concentration, due to the tightening
of the matrix microstructure.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction to health issues, especially hypertension (Goulding, 1997; Law,

The addition of salt to cheese serves a number of purposes. Salt
improves the flavour, texture and colour of cheese, it kills off the
starter cultures employed in the cheese-making process preventing
further growth and acid development, and it also helps to adjust
the moisture content of cheese by forcing moisture out (Fitzgerald
& Buckley, 1985; Payne & Morison, 1999). In addition, salt is
essential for the normal functioning of the human body, even
though the exact amount required by humans has proved difficult
to assess. The current dietary guideline for sodium for the general
public is no more than 2.4 g/day, equivalent to 110 mmol Na/d or
6.0 g NaCl (Kaplan, 2000). However, the average total daily sodium
intake by populations in developed countries is 10–12 g of NaCl
(Dillon, 1987; IFT, 1980), which is up to 25 times greater than the
minimum adult requirement (Al-Otaibi & Wilbey, 2006). Thus, any
treatment involving a further addition of salt to the diet might lead
* Corresponding author. Tel.: þ33 02 23 48 54 52; fax: þ33 02 23 48 55 78.
E-mail address: Juliane.Floury@agrocampus-ouest.fr (J. Floury).
1997). Many people on sodium restricted or health-oriented diet
avoid cheese consumption because of its high sodium content. For
example, Feta cheese has a high sodium content of
1.1  0.1 g 100 g1 (USDA, 1976), mainly due to its storage in brine.
Scientific data (O’Shaughnessy & Karet, 2004) suggest that the
effect of salt excess in the diet on hypertension development and
cardiovascular diseases constitutes an important public health
issue. Consequently, public health organism recommendation is to
gradually decrease salt consumption along the next years (AFSSA,
2002). The most concerned foods are bakery, pork meat products,
soups and cheeses. In this frame, the main question is how sodium
chloride quantity in food can be reduced without altering accept-
ability. One solution could be the partial sodium chloride substi-
tution by another compound with salty taste characteristics.
Nevertheless, attempts of replacement of sodium chloride by non-
sodium salts in cheeses failed because of an excessive bitterness
(Chamba & Debry, 1994; Fitzgerald & Buckley, 1985). Another
solution could be to decrease sodium concentration and to enhance
salty perception with other flavour compounds (odour or

0023-6438/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.lwt.2009.06.002
1622 J. Floury et al. / LWT - Food Science and Technology 42 (2009) 1621–1628
trigeminal compounds). Due to taste defect induced by the first
option and in order to lead to a generic approach, which can be
transposed to several food products, we choose to work on the
second option. However, a better understanding of electrolytes
distribution and mobility in the product, the salt release mecha-
nisms from the food matrix and the possibilities of enhancing salty
taste by other perception modalities using psychophysical data are
needed to propose new foods with reduced sodium chloride
content and high acceptability.
The aim of the present study is to better identify functional
factors and mechanisms implied in salt perception. The micro-
scopic structure of food significantly affects its processing charac-
teristics, flavour release and texture. Food microstructure studies
thus provide a key to understanding, and, therefore, controlling
food behaviour.
The mass transport between the solid food and the soaking
solution, is generally controlled by the diffusion rate of solutes in
the foodstuff. Diffusion velocities are calculated using effective
diffusion coefficients of solutes into the solid (Luna & Bressan, 1986;
Schwartzberg & Chao, 1982; Turhan & Kaletunç, 1992). For many
years some authors have reported various experimental studies
related to brining phenomena concerning different cheese varie-
ties: for camembert (Hardy, 1983), for fynbo (Zorrilla & Rubiolo,
1994), for cuartirolo (De Piante, Castelao, & Rubiolo de Reinick,
1990; Luna & Bressan, 1987), for romano (Guinee & Fox, 1983), for
feta (Turhan, 1996; Turhan & Kaletunç, 1992), for cheddar (Morris,
Guinee, & Fox, 1985), for gouda (Geurts, Walstra, & Mulder, 1974;
Geurts, Walstra, & Mulder, 1980; Luna & Chavez, 1992), and for
Emmental cheeses (Chamba, 1982; Pajonk, Saurel, & Andrieu,
2003). A review of diffusion of salt and moisture within a variety of
cheese was given by Guinee and Fox (1987). Most authors have
found that the change in the water content of cheese was linked to
the diffusion rate of salt (Payne & Morison, 1999).
The majority of the work published in this field relate to the
diffusion of sodium chloride and/or potassium chloride in cheese,
without ever considering the migration of other ionic solutes
during the brining process. Moreover, those papers only report the
transfer of sodium chloride followed by an evaluation of either
chloride ion or sodium ion without any validation with the counter
ion. Only a few works were carried out on soft or semi-soft cheeses.
The aim of this project was to study the influence of the char-
acteristics of complex lipoproteic matrices on the transfer of
aqueous solutes, by focusing the problem on model cheeses.
Indeed, a real cheese matrix is a rather more complex system. For
a better understanding of the fundamental phenomena, it appears,
therefore, more suitable, in a first approach, to mimic the real
system by using a model matrix containing protein and fat. In the
first part of this paper (Floury et al., in press), model lipoproteinic
matrices that could model cheese products presenting different
textural properties have been developped, in order to further study
the factors implied in the salt release in mouth during food
chewing. The manufacture of these products was perfectly
controlled and reproducible. Composition factors such as dry
matter, fat (dry basis), salt contents and pH, were varied in order to
modify physico-chemical, textural and structural characteristics,
which were perfectly characterised. The textural characteristics and
rheological properties of the model lipoproteinic matrices were
affected by their structural characteristics. Results of this work are
reported in Floury et al., 2009).
The second phase of the project consists in physical and
modelling approaches to better understand the transfer
phenomena of the aqueous solutes (salt, water and other ionic
solutes like lactates, phosphates, calcium, etc.) from the model
cheese during its consumption in the mouth. Concentration profiles
of several ionic species (sodium, chloride, lactates, citrates,
phosphates, calcium and potassium) were experimentally
measured inside different model cheese matrices during the
release of salt from the product in contact with artificial saliva at
constant temperature. The apparent diffusion coefficients of the
sodium chloride corresponding to the different model cheeses
were then determined by fitting the experimental concentration
profiles to the second Fick’s law.
2. Materials and methods
2.1. Experimental procedure
The experimental device was chosen in order to be able to
consider unidirectional solute mass transfers from the cheese
samples to the saliva (Fig. 1). The solution of artificial saliva was
adapted from the formula of Van Ruth, Roozen, and Cozijnsen
(1994) with the ingredients shown in Table 1. Sodium carbonate
was replaced by a phosphate buffer (0.1 mol L1, pH 7) because the
pH was not stable using the sodium carbonate. CaCl2 was also
removed from the solution because it precipitated. The ionic force
of this solution was equal to 117 mmol L1.
Cheese matrices were moulded and coagulated in impermeable
plastic cylinders 3 cm in diameter and 10 cm length. The plane
surface was put in contact with 8 L of artificial saliva (Fig. 1). This
volume was chosen because it allowed considering as constant the
solute concentrations in the saliva during all the experimental time
(solute concentrations were daily checked). The solution of saliva
was subjected to a sharp agitation thanks to a blade agitator in
order to be able to neglect the external resistance to mass transfer
in the boundary layer at the surface of the cylinder (results not
shown). The temperature and the relative humidity of the ambient
air were controlled and were, respectively, fixed equal to 15  C and
75%. An aluminium foil was finally laid out at the top of the
experimental device to avoid the evaporation of the solution and to
allow maintaining the full contact between the plane surface of the
matrices and the saliva over the test duration (6 days).
Five different model cheese were chosen among the full
experimental design studied in Floury et al., in press, whose
compositional factors are reported in Table 2. Those matrices were
chosen because we showed in the previous study that they present
different structural and textural properties which can then influ-
ence mass transfer properties of the solutes. Preparation of the
cheese samples is fully described in Floury et al., in press. Briefly,
the manufacture of the matrices can be described as follow: milk
protein concentrate powder was dissolved in pure water and then
homogenised with the required anhydrous milk fat concentration.
Glucono-delta-lactone or sodium hydroxide were added to the mix
before rennet coagulation to adjust the pH value and then control
the final structure of the model cheese.
cylindrical cheese
sample
x
15°C
75%HR
agitator
C(x,t)
0
flow of flow of
solution of Cs NaCl moisture
artificial saliva
Fig. 1. Diagram of the experimental device located in a controlled temperature and
relative humidity room.
 J. Floury et al. / LWT - Food Science and Technology 42 (2009) 1621–1628
Table 1
Artificial saliva composition adapted from Van Ruth et al. (1995).
Substance
NaH2PO4-H20 (Merck)
K2HPO4 (Merck)
NaCl (Fisher Scientific)
KCl (Panreac)
NaN3 (Merck)
a
In distilled water adjusted to pH 7.0.
Periodically, two cylindrical samples of cheese were simulta-
neously removed from the experimental device in order to be able
to duplicate the physico-chemical analysis. Beginning with the
matrix side that has contacted the saliva solution, cheese cylinders
were cut into about 2 mm slices. The thicknesses of the slice were
precisely measured with a calliper rule. Water content and ionic
concentrations were then measured from the slices. The full
experiment was duplicated for the two following product compo-
sitions: 370/20/1.5/6.2 and 370/20/0.5/6.5 (dry matter g/kg, fat (dry
basis) g/100 g, salt contents g/100 g and rennet pH) in order to
check the reproducibility of the mass transfer phenomena.
Moisture content was obtained at 102  C for 7 h using an air-
oven by drying duplicate samples under atmospheric conditions
(IDF, 1987).
Cation concentrations (sodium, potassium and calcium) were
measured from ashes dissolved in HCl (1 mol L1 solution) followed
by atomic absorption spectrometry (Varian AA300 spectrometer,
Les Ulis, France) according to Brulé, Maubois, and Fauquant (1974).
Ionic concentrations (chloride, phosphate and citrate) were
deduced from ionic chromatography after extraction. For this
extraction, around 0.5 g of cheese was put in approximately 5 mL of
osmosed water, homogenised 1 min with an Ultraturrax apparatus.
The mixture was held for 2 h at 40  C in a controlled water bath and
then cooled to 4  C. In order to eliminate any protein of the ana-
lysed solution that could damage the column, 500 ml of these
extract were added to 500 mL of a 6 mL/100 mL acid sulfosalicylic
solution. Solutions were stored at 4  C during 30 min before being
centrifuged at 6000 g during 5 min (EppendorfÒ Microcentrifuge
5415C, Hamburg, Germany). The supernatant is collected and
analysed according to Gaucheron, Le Graet, Piot, and Boyaval (1996)
in a high-performance liquid chromatography (Dionex DX-500
system, Jouy-en-Josas, France). Ionic concentrations were
expressed in mole per kg of cheese or in mole per kg of cheese
aqueous phase.
All these analytical measurements were done in duplicate.
Standard deviations of these analytical methods were less than 1%.
Local water and solutes concentrations were represented vs. the
distance from the centre to the surface of the different model
cheeses on the x-axis for different contact times between the saliva
solution and the cheese samples. The sodium and chloride
concentration profiles were compared to the predicted values
obtained from mathematical modelling of the coupled mass
transfer phenomena involved during the process.
Table 2
Composition of the model lipoproteinic matrices.
Product code DM g kg1 Fat/DM g/100 g Salt g/100 g
370/20/1.5/6.2 370 20 1.5
370/40/1.5/6.2 370 40 1.5
440/20/1.5/6.2 440 20 1.5
370/20/0.5/6.2 370 20 0.5
370/20/0.5/6.5 370 20 0.5
1623
2.2. Determination of NaCl effective diffusion coefficient values
Concentrationa For foodstuffs with a heterogeneous structure, it is often difficult
0.1 mol L1 to know exactly the volume into which the solute can penetrate and
0.1 mol L1 the path of migration. Nevertheless, the movement of solutes can
15 mmol L1 adequately be described as a diffusion process using an apparent or
6.4 mmol L1
effective diffusion coefficient (Gros & Rüegg, 1987; Loncin, 1980). In
0.005 g/100 g
a fundamental study of the penetration of salt into cheese, which is
accompanied by an outward migration of water, Geurts et al. (1974)
defined and determined an apparent diffusion coefficient for salt in
cheese moisture. They concluded from their results that the
movement of salt in cheese could be properly described as a diffu-
sion process. In the present study, the two fluxes of salt and water
are reversed but we made the hypothesis that the migration
mechanisms were similar: while the salt is released from the
cheese into the saliva, there is a simultaneous uptake of water from
the solution. When assuming no convective fluxes, the Fick’s
diffusion equation describing unsteady state mass transfer can be
written as:
vC
¼ VðD,VðCÞÞ (1)
vt
where C represents the Na or Cl ionic concentration in the cheese
(mol kg1), t is the time (s) and D the effective diffusion coefficient
of NaCl in the cheese (m2 s1).
Considering both unidirectional mass transfer along the x-axis
and a constant diffusion coefficient value, the previous equation
becomes:
vCðx; tÞ
¼ D,V2 ðCðx; tÞÞ (2)
vt
With the following initial and boundary conditions:
t ¼ 0 Cðx; 0Þ ¼ C0
where C0 is the initial Na or Cl ionic concentration in the cheese
(mol kg1).
It was assumed that the saliva solution in contact with the
cheese was well mixed and of constant composition. The boundary
condition imposed at the interface was that the cheese composition
was entirely replaced by the saliva solution at the bulk
composition:
t>0 Cð0; tÞ ¼ Cs and CðN; tÞ ¼ C0
where Cs is the Na or Cl concentration in the artificial saliva
solution.
The identification of the NaCl diffusion coefficient values from
our mass transfer experiments was performed by solving the
analytical solution of the Fick’s diffusion equation (Crank, 1975)
which can be written as:
 
Cðx; tÞ  CS x
¼ erf pffiffiffiffiffiffiffiffi (3)
C0  CS 2 D,t
Furthermore, we can consider the cheese sample as isothermal
and as a semi-infinite medium if the Fourier’s number value, F0 ¼
D  t=L2 is less than 0.05 where L is the sample length along the
diffusion direction, noted x (Pajonk et al., 2003). The unknown
parameter D was fitted for each experiment using a Matlab version
pH 7.0 algorithm. Values of this unknown parameter were fixed by
6.2
minimizing the root-mean-square error (RMSE) function using
6.2 a Matlab dedicated function called fminsearch. This function uses
6.2 the direct simplex search method (Lagarias, Reeds, Wright, &
6.2 Hubinger, 1998). The following (RMSE) function was calculated for
6.5
the different ionic concentrations using:
1624 J. Floury et al. / LWT - Food Science and Technology 42 (2009) 1621–1628
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u N  2
uX
RMSE ¼ t k  Ck
Cest exp
k¼1
where N is the total number of concentration measurements
considered for a given experiment, Cest is the concentration esti-
mated by the numerical solution, Cexp is the experimental
concentration value.
2.3. Statistical test
The simulated NaCl concentrations were compared to the
experimental results by the percentage of deviation (Bona et al.,
2007; Gerla & Rubiolo, 2003), in order to assess the goodness of fit.
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u N   2
u 1 X C est  C exp
%deviation ¼ 100t
N1 C exp k
k¼1
where C est is the mean concentration estimated by the numerical
solution; C exp , the experimental mean and N, the number of
observations considered.
Simulated values of the apparent diffusion coefficients values
obtained for the five different matrix compositions were statisti-
cally compared thank to a Least Significant Difference test at 85%
confidence interval.
3. Results and discussion
3.1. Are Naþ and Cl simultaneously diffusing?
Some typical experimental data for the sodium and chloride
concentration profiles inside a model cheese matrix (370 g/kg dry
matter, 20 g/100 g fat (dry basis), 1.5 g/100 g salt, pH 6.2) are pre-
sented on Fig. 2. It also shows the reproducibility of the ionic
concentration profiles for the same matrix composition, with the
three different symbols corresponding to three different experi-
mental runs. As the profiles were well superimposed, it can be
concluded that the reproducibility of the method was good.
However, the reproducibility could not be precisely calculated with
statistical tools because distances of migration were variable from
one experimental run to another, due to different slice thickness
corresponding to each experiment. Pajonk (2001) showed that the
reproducibility of the sodium chloride concentration profiles was
around 5–7% with its experimental setup.
It was also important for us to check if considering the salt
concentration thanks to the measurement of one of the ionic
species only, Naþ or Cl, is a valid hypothesis. Indeed, one of the co-
ions, for example the sodium could have been retained by the
negatively charged casein micelles, exchanging with the calcium
ionic species. However, all published studies found up to now
concerning the transport of salt in cheeses present NaCl concen-
tration profiles obtained thanks to the experimental determination
of only the sodium or the chloride species. Fig. 2 shows that the two
co-ionic species Naþ and Cl seem to diffuse together as their
respective concentration profiles are well superimposed. Consid-
ering the salt concentration thanks to the analysis of either Naþ or
Cl is then a valid hypothesis. The two sodium and chloride ionic
concentration data will be used here to determine the apparent
diffusion coefficient of salt in the different model cheese matrices.
3.2. NaCl diffusion coefficient identification
For all the diffusion experiments, we used the basic mass
diffusion equation with constant diffusivity (Eq. (2)) to identify
the effective NaCl diffusivities values of the different cheese
(4) matrix compositions. Fig. 3 shows the typical experimental and
theoretical profiles of concentration of salt obtained with one of
the model matrix composition (370 g kg1 dry matter, 20 g/100 g
fat (dry basis), 1.5 g/100 g salt, pH 6.2). Apparent diffusion coef-
ficients and the percent deviation values of the other cheese
matrices are reported on Table 3. As shown in Table 3, the mean
percent deviation calculation is done of two different manners:
with the full set of data, and without the first slice in contact with
the artificial saliva. Indeed, the difference between the theoretical
and the experimental concentrations is very important in this first
slice, causing an overestimation of the deviation value (around
10%). The percent deviation values obtained without considering
the first cheese slice showed that theoretical and experimental
data agreed closely validating the proposed theoretical model.
Our experimental set of data is correctly fitted by a constant
(5) diffusion coefficient value with respect to the migration times,
leading to the conclusion that the D-values can be considered as
concentration invariant. This result is contradictory with the
conclusions of Pajonk et al. (2003) and Turhan (1996), who
showed that a constant diffusion coefficient model is not able to
interpret precisely the NaCl diffusion kinetics during the brining
process of, respectively, neither a soft cheese like white cheese
nor a hard cheese like Emmental. However our results are
consistent with other published studies, in which NaCl diffusion
transport processes inside the cheese material during classical
brining are often described by using the second Fick’s diffusion
law, considering the diffusion coefficient as constant (Geurts et al.,
1974, Gros & Rüegg, 1987; Guinee & Fox, 1983; Luna & Bressan,
1987; Zorrilla & Rubiolo, 1994).
Values of the apparent diffusion coefficients corresponding to
the transport of salt during its release from the model cheese into
the saliva solution presented in Table 3 are included between 2.81
and 3.43  1010 m2 s1 at 15  C and 75% HR, depending on the
matrix composition. Our results are of the same order of magnitude
as published diffusion coefficients measured during brining of
cheeses. For example, in a soft type cheese like Cuartirolo Argentino
cheese (48 g/100 g dry matter, 51.6 g/100 g fat (dry basis)), Luna
and Bressan (1987) proposed an NaCl diffusion value during the
brining and ripening of 3.6  1010 m2 s1 at 7.5  C, and in a semi-
hard cheese like Fynbo cheese (48 g/100 g dry matter, 29 g/100 g
fat (dry basis)), Zorilla and Rubiolo (1994) determined a salt
diffusion coefficient equal to 4.14  1010 m2 s1 during its ripening
at 12  C and 90% relative humidity. In white cheese, a semi-hard
ripened variety traditional to Turkey (45 g/100 g dry matter, 42 g/
100 g fat (dry basis)), Turhan (1996) estimated that salt diffusivities
were included between 2.2 and 3.7  1010 m2 s1 at 4  C, and 3.9
and 4.2  1010 m2 s1 at 20  C, depending on the salt content of
cheese. D was found to be about 2.3  1010 m2 s1 at 12.6  C in
a full-cream model cheese containing 55–60 g/100 g dry matter
(Geurts et al., 1974). D-values reported by other authors (Guinee &
Fox, 1983; Hardy, 1983; Morris et al., 1985; Walenta, 1985) range
from about 1.4 to 3.1 1010 m2 s1, depending mainly on dry
matter content and temperature but also to some extent on fat-to-
non-fat solids ratio (Geurts et al., 1974; Guinee & Fox, 1983), brine
composition (Geurts et al., 1980; Morris et al., 1985), proteolysis,
calcium content and homogenisation of milk (Guinee & Fox, 1983).
3.3. Influence of different factors on the salt diffusivity
The difference between the D-values obtained with several
matrix compositions could be related to their microstructural and
textural properties, which are reported in the first part of this paper
(Floury et al., 2009).
 J. Floury et al. / LWT - Food Science and Technology 42 (2009) 1621–1628 1625

1 day 2 days
1 1

0,8 0,8

C-Cs/C0-Cs
C-Cs/C0-Cs
0,6 0,6

0,4 0,4

0,2 0,2

0 0
0 20 40 60 0 20 40 60
x (mm) x (mm)

3 days 6 days
1 1

0,8 0,8
C-Cs/C0-Cs

C-Cs/C0-Cs
0,6 0,6

0,4 0,4

0,2 0,2

0 0
0 20 40 60 0 10 20 30 40 50
x (mm) x (mm)

Fig. 2. Naþ and Cl diffusion profiles of the matrix 370 g kg1 dry matter; 20 g/100 g fat (dry basis); 1.5 g/100 g salt; rennet pH 6.2 after 1, 2, 3 and 6 days of contact with the solution
of artificial saliva. Naþ: empty symbols, Cl: plain symbols. The three different geometries of symbols (,, 6, B) correspond to three different experimental runs.

3.3.1. Effect of fat content 3.3.3. Effect of the pH

As shown in Table 3, the effect of the fat (dry basis) is negligible
as the apparent diffusion coefficients determined from the salt
concentration profiles in matrices 370/20/1.5/6.2 and 370/40/1.5/
6.2 are non-significantly different. It seems that there is no tortu-
osity effect due to the fat droplet distribution in our model cheese
matrix on the diffusion rate. This result is in contradiction with
Geurts et al. (1974), who observed that for cheeses with equal
moisture content, salt diffusivity increased with fat in dry basis.
They also reported that data in the literature which allow checking
their observations were scarce.
Experiments conducted with two model cheese matrices with
similar dry matter (370 g kg1), fat in dry basis content (20 g/100 g),
salt level (0.5 g/100 g) but different pH at renneting varying from
6.2 to 6.5 show that pH has a significant influence on the apparent
diffusion coefficient of the salt (Table 3) that increases from 2.81 to
3.26 (0.07)  1010 m2 s1, which means an increase of 16%. This
result is not in agreement with published studies concerning

3.3.2. Effect of the dry matter content (DM)

It is common knowledge that from two cheeses of a similar type,
the one with the higher moisture content absorbs salt more rapidly,
but this does not mean a higher diffusional mobility (Geurts et al.,
1974). We measured a significant effect of the dry matter content of
the matrices on the apparent salt diffusion coefficient. As reported
in Table 3, when the dry matter content increased from 370 to
440 g kg1 in the two model cheese matrices with similar fat in dry
basis content (20 g/100 g), salt level (0.5 g/100 g) and pH (6.2), the
apparent salt diffusion coefficient decreases from 3.43 (0.21) to
3.02  1010 m2 s1, which means a decrease of 12%. Geurts et al.
(1974) also reported that within one series of cheeses with equal fat
in dry matter, the apparent diffusivity strongly depends on initial
moisture content. They measured a decrease by a factor of 2.5 of the
D-value when the dry matter increased from 500 to 640 g kg1. As
reported in the part 1 of this paper (Floury et al., in press), the
microstructure of the proteinic networks was much branched and
exhibited a high degree of cross-linking in the cheese matrix con- Fig. 3. Modelling of the sodium chloride concentration profiles of the matrix
370 g kg1 dry matter; 20 g/100 g fat (dry basis); 1.5 g/100 g salt; rennet pH 6.2 at
taining the highest protein concentration. The microstructure of different diffusion times with a constant diffusivity coefficient D ¼ 3.09  1010 m2 s1.
the matrices with higher moisture content was coarser and fluffier, Experimental values were obtained from three different experiments (+ day 1; day
thus facilitating the diffusion of salt by limiting friction effect. 2; day 3; day 6), Model (lines).
1626 J. Floury et al. / LWT - Food Science and Technology 42 (2009) 1621–1628
Table 3
Diffusion coefficients of salt determined with different model cheese compositions.
Matrix composition DM (g kg1)/Fat Diffusion coefficients Mean diffusion coefficients
(dry basis) (g/100 g)/Salt (g/100 g)/pH (1010 m2 s1) (1010 m2 s1)
370/20/1.5/6.2 (1) 3.63 3.43*
370/20/1.5/6.2 (2) 3.23
370/40/1.5/6.2 3.26 3.26
440/20/1.5/6.2 3.02 3.02
370/20/0.5/6.2 2.81 2.81*
370/20/0.5/6.5 (1) 3.34 3.26
370/20/0.5/6.5 (2) 3.19
*Significantly different (P < 0.15).
cheese salting (Geurts et al., 1974; Guinee & Fox, 1983) which
reported that despite differences in textural characteristics of the
cheeses, the D-values were almost equal. Geurts et al. (1974) sug-
gested that surface area and hence pore width of the protein matrix
did not change with the pH within the limits applied. However, the
pH range studied in the current study (6.2–6.5) is much higher than
that (4.7–5.7) in the study of Geurts et al. (1974); pH-related casein
swelling and texture/structure are then likely to differ markedly
between the lipoprotein matrices and the cheese. Moreover, in the
current study, the pH at renneting is equal to the final pH of the
cheese. In the study of Geurts et al. (1974), the pH is varied with
starter culture after rennet addition. Differences in pH range and in
the mode/stage of pH variation are likely to have many indirect
effects (in addition to pH) on casein hydration/aggregation, casein
hydrolysis, which in turn could have differing effects on the Naþ Cl
diffusivity. As reported in Floury et al. (in press), the effect of the pH
at renneting was significant on the structural and textural proper-
ties of the model cheese matrices. They measured a significant
increase of the hardness and the springiness of the matrix, as well
as a reduction of its adhesiveness. Increasing the pH at renneting
allows a better hydration of the casein micelles because of the
higher negative charges (Famelart, Lepesant, Gaucheron, Le Graet,
& Schuck, 1996) and thus a better solubilization of proteins, which
would facilitate the diffusion of salt.
3.3.4. Effect of the initial salt concentration of cheese
The salt content initially present in the model matrices signifi-
cantly influences the value of the NaCl diffusion coefficient which,
respectively, decreases from 3.43 (0.21) to 2.81 1010 m2 s1 in
matrices 370/20/1.5/6.2 and 370/20/0.5/6.2, which means a decrease
of 18%.
As shown in part 1 of this paper (Floury et al., 2009), the effect of
salt on the structural and textural properties of cheese is complex.
Reduction of the initial salt content in the matrix led to changes in
the composition and geometrical arrangement of the casein
network, which were followed by significant modifications of the
texture profiles of the cheeses: an increase of the hardness and the
cohesiveness, and a decrease of the adhesiveness were measured.
This probably means that the microstructure of the matrix is
tightened by the reduction of the salt content, consequently
limiting its diffusivity in the product. Geurts et al. (1974) reported
a decrease in the apparent mean diameter of the protein particles
with salt concentration, equivalent to a decrease in the effective
pore width of the matrix.
3.4. What about the transport of the other ionic species?
Most solid foods show complex structure with cellulosic or
proteic framework that occludes an aqueous solution with major
and minor components. Minor concentration solutes have an
important role in food characteristics, which are associated with
the quality of the product and its preservation. However, the
Standard Error of the Mean Mean percent deviation %
(1010 m2 s1)
Considering all slices Without first slice
0.154 13.5 12.9
16.1 12.7
0.218 16.2 13
0.218 21.5 14.5
0.218 22 17.5
0.154 21.7 16.3
20.7 14.1
diffusion rate for the components in minor quantities during
leaching or infusion processes in foods was almost not modelled
(Gerla & Rubiolo, 2003). Models of solute diffusion in solid–liquid
systems were generally developed for the component with larger
concentration or for a group of solutes considered as one pseudo-
component, without considering the minor solutes. According to
this, pseudobinary diffusion models of the mass transfer process
were used to calculate the main solute flux and the diffusion
coefficient as a binary solute–solid system (Bailey, 1975; Bressan,
Carroad, Merson, & Dunkley, 1981).
In parallel to the study of the sodium chloride migration during
the release of salt from the model cheeses in contact with artificial
saliva at constant temperature, the concentration profiles of several
other minor ionic species (citrates, phosphates, calcium and
potassium) were also measured. Via the determination of their
transport properties, we wanted to check if there were synergies or
inhibitions of the diffusion of salt due to of the presence and/or the
migration of the other ionic species.
Typical concentration profiles obtained with one of the matrix
composition (370/20/1.5/6.2) are shown in Fig. 4a. Fig. 4b shows the
concentration profiles of the ionic species obtained with the same
model cheese composition in contact with pure water instead of
the artificial saliva solution. Results obtained with the other matrix
compositions (Table 2) are not shown because the concentration
profiles were not significantly differentiable from the matrix 370/
20/1.5/6.2. Indeed, as shown on Fig. 4, measured concentration of
the other cheese ionic species are low compared to sodium and
chloride concentrations. Fig. 4 also shows that the points are much
scattered all over the graph, because of the large variability of the
results. The concentration of the minor ionic species was not
sufficient to obtain a precise determination that could allow us to
model their respective apparent diffusion coefficients. However,
Fig. 4 allows getting a good general survey of the behaviour of the
minor ionic species during the release of salt from the model
cheeses in contact with either artificial saliva or pure water. Con-
cerning the calcium, there is no difference between the two graphs,
because the concentration of calcium is null in both artificial saliva
solution and pure water. Concentration profiles are quite super-
imposed whatever the migration time, except near the contact
surface where the concentration gradient is very strong between
the two phases. As shown in part 1 of this study (Floury et al., in
press), only 10–20% of the total calcium is soluble in the aqueous
phase of the model matrix. The calcium does not diffuse much from
the proteinic matrix into the aqueous solutions because the
majority of this ionic species is fixed to the casein micelles (80–90%)
and then is not available to transfer from the cheese matrix into the
saliva solution.
Concerning the behaviour of the potassium ionic species, as
shown in Fig. 4, when the matrix is in contact with the saliva solution,
as the potassium concentrations are quite similar in both the matrix
and in the saliva, the concentration gradient is very low and then the
mass transfer rate is also weak. However, when the product is in
 J. Floury et al. / LWT - Food Science and Technology 42 (2009) 1621–1628 1627

a b
Matrix 370/20/1.5/6.2 - water solution Matrix 370/20/1.5/6.2 - saliva solution
0,1 0,1

Phosphates (mol.kg-1cheese)
Phosphates (mol.kg-1cheese)
0,08 0,08

0,06 0,06

0,04 0,04

0,02 0,02

0 0
0 10 20 30 40 50 0 10 20 30 40 50
x (mm) x (mm)

Matrix 370/20/1.5/6.2 - water solution Matrix 370/20/1.5/6.2 - saliva solution

0,16 0,16

Calcium (mol.kg-1cheese)
Calcium (mol.kg-1cheese)

0,14 0,14
0,12 0,12
0,1 0,1
0,08 0,08
0,06 0,06
0,04 0,04
0,02 0,02
0 0
0 10 20 30 40 50 0 10 20 30 40 50
x (mm) x (mm)

Matrix 370/20/1.5/6.2 - water solution Matrix 370/20/1.5/6.2 - saliva solution

0,1 0,1
Potassium (mol.kg-1cheese)
Potassium (mol.kg-1cheese)

0,08 0,08

0,06 0,06

0,04 0,04

0,02 0,02

0 0
0 10 20 30 40 50 0 10 20 30 40 50
x (mm) x (mm)

Matrix 370/20/1.5/6.2 - water solution Matrix 370/20/1.5/6.2 - saliva solution

0,05 0,05
Citrate (mol.kg-1cheese)
Citrate (mol.kg-1cheese)

0,04 0,04

0,03 0,03

0,02 0,02

0,01 0,01

0 0
0 10 20 30 40 50 0 10 20 30 40 50
x (mm) x (mm)

Fig. 4. Typical concentration profiles of other ionic solutes (calcium, potassium, phosphate and citrate) in the model cheese matrix 370 g kg1 dry matter; 20 g/100 g fat (dry basis);
1.5 g/100 g salt; rennet pH 6.2 during the contact with (a) artificial saliva, (b) pure water (+ day 1; day 2; day 3; day 6; – concentration in saliva).

contact with pure water, there is a non-negligible flux of potassium mostly present in the soluble phase (Floury et al., 2009), facilitating
from the cheese matrix into the water. The difference between the their migration process. The same observation as for the calcium can
migration behaviours of Ca2þ and Kþ is due to the fact that the be made concerning the transport of phosphate and citrate species.
calcium is quite strongly retained in the proteic network formed by Fig. 4 shows that their concentration profiles stay relatively constant
casein micelles, whereas the other ions like Naþ, Cl and Kþ are with the migration time and the distance from the surface, except at
1628 J. Floury et al. / LWT - Food Science and Technology 42 (2009) 1621–1628
the water proximity where the concentration gradient between the
solution and the cheese matrix is very important. These ionic species
are not migrating in the cheese matrix because they are strongly
bounded to the lipoproteinic network.
4. Conclusion
The mass transfer occurring during the release of salt from
different model cheese matrix composition into artificial saliva is
mathematically modelled as an effective diffusion process. The
variation of the diffusion coefficient values of salt with respect to
the matrix compositions is linked to their structural and textural
properties. The concentration profiles of several other minor ionic
species (lactates, citrates, phosphates, calcium and potassium) are
also measured. Despite the fact that accurate results are difficult to
obtain, concentration profiles are explained from a qualitative point
of view. Future work will consist of a better understanding and
modelling of mass transfer phenomena of these minor ionic
species, in order to integrate possible interaction phenomena with
the matrix and the sodium chloride to the diffusion process.
Acknowledgements
The authors thank the French National Food Project (PRA 2005)
for their financial support.
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