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Food Science and Technology

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Influence of roasting on the water sorption isotherms of nuts / Influencia del tueste sobre las
isotermas de sorcin de agua de diferentes frutos secos
N. Martnez-Navarrete and A. Chiralt
Food Science and Technology International 1996 2: 399
DOI: 10.1177/108201329600200606
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399-

Influence of

the water
isotherms of nuts

roasting

on

sorption

Influencia del tueste sobre las isotermas de sorción


de agua de diferentes frutos secos
N. Martínez-Navarrete and A. Chiralt*

Departamento de Tecnologia de Alimentos,

Universidad Politécnica de Valencia,


Correos 22012, 46071 Valencia, Spain

Apdo.

This work studies the influence of the roasting process on sorption isotherms of almond, hazelnut
and peanut over the normal range of storage temperatures (5, 25 and 45 °C) The results obtained
showed that water sorption properties of unroasted nuts are affected by fat content. The mono) increased when the nut fat content
s
layer moisture content and water affinity (sorption heat, Q
decreased. After roasting, a more homogeneous water affinity was observed for the different
products, although fat content still affected the monolayer capacity. Also, roasting reduced monolayer moisture content and Q
s values in each sample and made the moisturizing process less
spontaneous (decreasing the thermodynamic driving force). These results are consistent with an
increase of the hydrophobicity of the cellular components of nuts due to the enhancement of lipid
interactions. The water binding properties of active points in the roasted products were reduced

and, hence,

some

water

Keywords: roasting,

sorption

water

active

sorption,

points disappeared.

nuts

Se ha estudiado la influencia del tueste sobre las isotermas de adsorci6n de algunos frutos secos
(almendra, avellana y cacahuete) en un intervalo de temperaturas usual durante su almacenamiento y manipulacin (5, 25 y 45 C). Los resultados obtenidos mostraron que las propiedades
de adsorci6n del agua de los frutos secos crudos estan afectadas por el contenido en grasa. La
humedad de la capa monomolecular y la afinidad por el agua (calor de sorci6n, Q~) aumentan
cuando el contenido en grasa disminuye. Despu6s del tueste se observa un comportamiento mgs
homog6neo para todos los productos, aunque el contenido en grasa sigue afectando a la capacidad
de la monocapa. Ademas, el tueste reduce la humedad de la capa monomolecular y Q, para cada
muestra y hace el proceso de hLimectaci6n menos espoiitaneo (disminuyendo la fuerza impulsora
termodinamica). Estos resultados son coherentes con un aumento de la hidrofobicidad de los
componentes celulares de los frutos secos debido a que se potencian las interacciones lipidicas.
Los puntos activos.del producto reducen su capacidad de uni6n del agua y algunos de ellos

desaparecen.
Palabras clmm: tueste, adsorcin de agua, frutos

INTRODUCTION
Moisture content is one of the more relevant factors
which determines food quality. The moisture content
*
To 7vhoiii correspolldence shollld be sent.
Received 11 Jrrrm 1996; revised 25 July 1996.

secos

of a product, in relation to temperature, can exert an


influence on its chemical, microbiological and enzymatic stability (Labuza, 1980). In this sense, knowledge of water sorption characteristics is necessary to
predict shelf-life and to determine the critical water
activity and critical water content that define the
acceptability ranges of products. The sorption
isotherms allow us to model changes in the water

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400
content of

product during

its

storage. Moreover, sorption data

and
different temper-

manipulation
at

atures makes

thermodynamic analysis of the system


possible, providing information about the waterfood interactions throughout sorption heat values.
Determination of the thermodynamic parameters
allows for a fuller interpretation of the isotherms. The
sign of the free energy change (AG) provides a criterion for the spontaneity of the process (AG<0,
spontaneous). The change of enthalpy (i1H) measures the
energy changes occurring during the sorption process
and may be associated with the attractive or repulsive forces in the system (AH<0
signifies the existence
of attractive forces involved in the mechanism of
sorption). Entropy changes (AS) may be associated
with the spatial arrangements occurring at the watersorbent interface (JS<0
describes a more structured
system) (Apostolopoulos and Gilbert, 1990).
Nuts, either roasted or unroasted, are a widely
consumed product. One of the more important characteristics that defines acceptability, besides the
oxidation of lipids, is fracturability during mastication. In many cases these characteristics, which can
be influenced by water content, are lost with storage.
It is therefore important to study the moisture
content-water activity (a~~.) relationship over the range
of different temperatures at which the product is
stored
The objective of this work is to study the influence
of the roasting process on sorption isotherms of
almond, hazelnut and peanut over there usual storage
temperature range. Although different authors have
described isotherms for some of these raw products
(Lomauro et al., 1985; L6pez et al., 1995) the influence
of temperature change and the roasting process itself
has not been studied.

MATERIAL AND METHODS


As raw material for water vapour sorption experiments, three nuts, roasted and unroasted, were
studied: hazelnut (var. Negret) from Tarragona
(Spain), almond (var. Marcona) from Alicante (Spain),
and peanut (var. Virginia) from Valencia (Spain) were
provided by a commercial store in Valencia. The
roasting process was carried out in an air-forced oven
at 180 C for 15 min. Samples between 1 and 2 g of
each nut, previously cut into small pieces, were
hydrated at 25 C in hermetical chambers with known
and constant relative humidity (RH) (Greenspan,
1977), until constant weight was reached. Different
saturated salt solutions were used to achieve this:
LiBr (RH 6.4%) LiCI (RH 11.3%); KAc (RH 22.5%); NaI

(RH 38.2%); NaBr (RH 56.2%); CuCl, (RH 67.5%);


Nad (RH 75.3%). Each sample was equilibrated in
duplicate and the weight was determined periodically
until equilibrium was reached. The same experiment
was carried out at 5 and 45 C.
Initial water content (zv;) of all roasted and
unroasted nuts was determined in triplicate by the
Karl Fischer titration method (Scholz, 1988) in a
Mettler DL-18 Titrator. The equilibrium water content
of each sample (zv) was determined by weight difference, considering the Wi value of each product.
Fat content of raw products was analysed in triplicate by the Soxhlet method.

RESULTS AND DISCUSSIDN


The initial composition of the studied nuts is shown
in Table 1.
The water sorption isotherms (Figure 1) exhibited
a sigmoid shape described as a type II isotherm as
classified by Brunauer (1945). For each nut studied
there was a large difference between the isotherms
of unroasted and roasted products, the latter showing
a smaller capacity for water adsorption. This can be
explained by the chemical modification of proteins
associated with the denaturation phenomenon and
the enhancement of interactions with other components such as carbohydrates and lipids caused by
the roasting process (P6rez, 1995). In consequence,
an increase in protein hydrophobicity seems to take
place which means a decrease in the available sites
in the substrate for water adsorption. The greatest
differences between roasted and unroasted product
behaviour are observed at 5 C and are attenuated

Table 1. Moisture and fat contents of the roasted and


unroasted nuts.
Tabla 1. Contenido de agua y grasa de los productos
estudiados crudos (U) y tostados (R) Almendra (A), avellana (H) y cacahuete (P)

U
unroasted; R
peanut.
=

roasted; A

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almond; H

hazelnut; P

401

with

the increase in

temperature, especially for

(van den Berg and Bruin, 1981). An increase in


temperature causes physico-chemical changes that

The effect of temperature on physical adsorption


expected from the Clausius-Clapeyron approach

result in a loss of water sorption active points in the


substrate (Iglesias and Chirife, 1976). It is remarkable
that differences are more pronounced for unroasted
than for roasted products. In the latter products, the
isotherm at 5 C appears lower than would be
expected from data recorded at 25 and 45 C. In spite
of the length of time taken for the equilibration of
samples at low temperature (some months), the
isotherm of roasted products at 5 C could correspond
to a pseudoequilibrium situation, related to the low
water diffusivity in the more hydrophobic medium

peanuts.
is

as

produced by roasting.
For each temperature, the

peanut isotherm is

always above the isotherms of the other nuts, which


are largely similar for roasted products. This is in
agreement with the lower fat

content of peanuts.
Isotherm data were fitted to GAB (aw < 0.8) and
BET (aw < 0.4) models (Table 2). The monolayer moisture content value (it),,) supports the conclusions
drawn above in relation to the effects of roasting,
temperature and different product composition.
Using both models, Wo showed similar values,
although slightly smaller for the BET model. The
monolayer moisture content varies between 2.5 and
4.5ryo (kg water/100 kg dry solids, % w/dw) for
raw products and between 1.3 and 3.2% (w/dw) for
roasted ones. For most dry foods, the rate of lipid
oxidation is most rapid at low moisture content and
decreases when the humidity is increased (Labuza et
nl., 1970). In fact, the products stored at the lowest n.
(zve < ZVO) were the ones that had a clear rancid odour.
The values of C showed the greater water affinity
for raw samples, which always have higher C values
than the respective roasted ones. Differences due to
temperature and kind of nut were observed.
Nevertheless, the strong mathematical correlation
between the parameters, in both GAB and BET
models, and the associated high values of the standard errors of C, make the analysis of the influence
of these factors difficult. For this reason, the direct
analysis of the experimental data by means of the

1. Water sorption isotherms for: (a) almond,


(b) hazelnut and (c) peanut. Experimental data (open
symbols, raw nuts; closed symbols, roasted nuts) and

Figure

GAB fitted model.

Figura 1. Isotermas de adsorci6n de agua para la


almendra (a), avellana (b) y cacahuete (c). Puntos experimentales (simbolos huecos para los productos crudos
y rellenos para los tostados) y ajuste al modelo de GAB.

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402

Table 2.

Parameter values obtained from

fitting GAB and

BET models to isotherms of roasted (R) and unroasted

(U) nuts.
Tabla 2. Valores de los par6metros obtenidos del ajuste de los modelos de GAB y BET a las isotermas de los
diferentes productos estudiados. Almendra (A), avellana (H) y cacahuete (P), crudos (U) y tostados (R).

unroasted; R

roasted; A

almond; H

hazelnut; P

was considered to
model the temperature effect.
AH, plotted as a function of water content, is
presented in Figure 2. For the roasted product, only
data obtained at 25 and 45 C were used, as the
samples at 5 C could not be in equilibrium as
described above. All AH values were < 0 which indicates the existence of binding forces involved in the
sorption mechanism. These forces were greater for
unroasted than for roasted products as shown by the
higher values of -AH. The attractive forces increased
until a maximum was achieved at approximately 3%
(w/dw) for raw materials and 2% (w/dw) for roasted
ones. These values of water content are of the same
order as the monolayer moisture content, obtained
from the BET and GAB models in each case. From
this maximum, the active sites for the sorption of
water diminish and so -AH values decrease. The
monolayer sorption net heat (Q,), values obtained
were 22.7, 20.9 and 33.6 kJ/mol for the unroasted

Clausius-Clapeyron approach

peanut.

almonds, hazelnuts and peanuts, respectively, and


21.4, 19.5 and 19.5 kJ/mol for the roasted ones. Q, =
AH -

AH,.

water

(-43.96 kJ/mol

were

AH,,
at

is the heat of

evaporation

of

25 C).

The

negative ~1G values (Figure 3) describe the


spontaneity of the sorption process for both unroasted
and roasted nuts. The decrease in -AG when mois-

increased, approaching zero at high


levels, showed that maximum sorption capacity

ture content
water

could be reached for the material after which the


process was halted. The influence of water content on
the AG value was greater below a critical water level,
and almost became zero from this value onwards.
This can be associated with the binding of water in
active sites on the surface of the material. After the
saturation of these sites, at around 3% (w/dw) of
moisture for raw products and 2% (w/dw) for roasted
ones, the sorption process continues in the more abundant active sites with less reactivity. This point
supports that made for AH values.

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403

Figure

2.

Enthalpy of sorption (3FQ


for

as a

(a) and roasted (b)


almond; H = hazelnut; P peanut.

water content

raw

function of
nuts. A

2. Entalpia de adsorci6n (3FQ en func16n de la


humedad para los productos crudos (a) y tostados (b).
A
almendra; H avellana; P = cacahuete.

Figura
=

3. Gibbs free energy of sorption (JG) at 25 C


function of water content for raw (a) and roasted
(b) nuts. A almond; H
hazelnut; P peanut.

Figure
as a

Figura 3. Energia libre de adsorci6n (JG) a 25 C en


func16n del contenido en agua para los productos
crudos (a) y tostados (b). A
almendra; H avellana;
P
cacahuete.
=

The greater values of -3G at low moisture levels


for unroasted nuts point to the higher spontaneity of
the moisturizing process in these samples due to their
more hydrophilic properties. The faster -JG diminution for roasted nuts in relation to the increase in
water content indicates that a quicker saturation of
the water binding capacity of these samples occurs.
A change in the trend AS, similar to that showed
for AH, is observed near the monolayer moisture

value (Figure 4). The minimum AS value obtained at


around Wo indicates that a more structured system,
at molecular level, was effective at this point. The
roasting process affects the ~1S pathway and its
minimum value principally in peanuts, where a more
pronounced diminution of the minimum is observed
due to roasting. For roasted samples the influence of
the kind of nut on AS evolution was smaller than
for unroasted ones. This can be attributed to smaller

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404

differences in the degree of molecular organization in


the former products. This is more dependent on the
binding forces of active sites which were more homogeneous in roasted samples because of the enhancement of lipid interactions.

REFERENCES
Apostolopoulos D., Gilbert S.G. (1990). Water sorption of
coffee solubles by frontal inverse gas chromatography:
Thermodynamic Considerations. Journal of Food Science,
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55:
Brunauer S. (1945). The adsorption of gases and vapours.
Princeton. N.J. : Princeton Univ. Press.
Greenspan L. (1977). Humidity fixed points of Binary
Saturated Aqueous Solutions. Journal of Research of the
National Bureauof Standards-A. Physics and Chemistry. 81A
no 1: 89-96.
Iglesias H., Chirife J. (1976). Prediction of effect of temperature on water sorption isotherms of food material. Journal
of Food Technology 11: 109-118.
Labuza T.P. (1980). The effect of water activity on reaction
kinetics of food deterioration. Food Technology 51: 36-41.
Labuza T.P., Tannenbaum S.R., Karel M. (1970). Water content and stability of low moisture and intermediate moisture foods. Food Technology 24 (5): .543-550.
Lomauro C.J., Bakshi A.S., Labuza T.P. (1985). Evaluation of
food moisture sorption isotherm equations.Part II: milk,
coffee, tea, nuts, oilseeds, spices and starchy foods.
Lebensmittel-Wissenschaf und Technologie, 18: 118-124.
L&oacute;pez A., Pique M.T., Clop M. (1995). The hygroscopic
behaviour of the hazelnut. Journal of Food Engineering 25:
197-208.
P&eacute;rez I. (1995). Estudio de algunos cambios quimicos y
microestructurales producidos en el proceso de elaboraci&oacute;n del Turr&oacute;n de Jijona,. Tesis doctoral, Universidad
Polit&eacute;cnica de Valencia.
Scholz H. (1988). Karl-Fischer Titration in siedendem
Methanol Wasserbestimmung imRostbaffe. Deutsche
Lebensmittel-Rundschau 84 (3): 1-41.
Van den Berg C., Bruin S. (1981). Water activity and its estimation in food systems: theoretical aspects. In: Rockland
L.B., Stewart G.F. (eds), Water Activity: Influences on food
quality. London and New York: Academic Press. pp. 1-43.
-

Figure 4. Entropy of sorption (AS) at 25 C as a


function of water content for raw (a) and roasted (b)
products. A almond; H hazelnut; P peanut.
=

Figura 4. Entropia de adsorci6n (AS) a


funci6n del contenido en agua para los
crudos (a) y tostados (b). A
almendra; H
P
cacahuete.
=

25 C

en

productos
=

avellana;

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