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Kinetic study of lipid oxidation in roasted coffee

M.D. Ortolá, C.L. Gutiérrez, A. Chiralt and P. Fito
Food Science and Technology International 1998 4: 67
DOI: 10.1177/108201329800400109

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 67

Kinetic study of lipid oxidation in roasted coffee

11

Estudio cinetico de la oxidacion de lipidos en cafe tostado

M.D. Ortolá, C.L. Gutiérrez, A Chiralt* and P. Fito

Departamento de Tecnología de Alimentos, Universidad Politécnica de Valencia, Camino de Vera,

14.46022 Valencia, Spain

The kinetics of lipid oxidation in ground roast Arabica coffee from Colombia stored under differ-
ent conditions were studied. Rancidity was controlled by the analysis of the peroxide value at 30-
day intervals. The influence of moisture content (26 and 43 g/kg), storage temperature (5, 25
and 35 °C) and packaging conditions (with non-sealed bags, under vacuum, 35 mbar, and packed
under CO2 atmosphere) on the kinetics was determined. Experimental values were fitted with a
kinetic model for the mechanism of lipid oxidation. Lipid oxidation is described by two steps, which
implies a monomolecular and a bimolecular initiation mechanism for the first and second period
respectively. The kinetic constants showed that the plastificant effect of water and CO
2 lead to an
important change in the reactants’ mobility within the temperature range. However, the rise in
moisture content seems to protect the product from formation of the peroxide. Furthermore, this
effect is more important in the second step of the oxidation process.

Keywords: coffee, kinetics, oxidation, lipids

Se ha estudiado la cinetica de oxidaci6n lipidica de cafe tostado molido de origen Colombia,
almacenado en distintas condiciones. El enranciamiento de las muestras se control6 a trav6s del
analisis del indice de per6xidos a intervalos de 30 dias. Se determin6 la influencia que distintos fac-
tores tienen sobre la velocidad de oxidaci6n: humedad del producto (26 y 43 g/kg), temperatura
(5, 25 y 35° C) y condiciones de envasado durante el almacenamiento (bolsas abiertas, bolsas
envasadas a vacio, 35 mbar, y bolsas con atmosfera de CO,). Los resultados experimentales se ajus-
taron a un modelo cin6tico, segun el cual, la oxidaci6n de lipidos tiene lugar en dos etapas, las
cuales implican mecanismos de iniclaci6n monomoleculares y bimoleculares, respectivamente. Las
constantes cin6ticas obtenidas reflejaron un importante papel plastificante del agua y del CO2,
que se tradujo en un cambio en la movilidad de los reactantes en el intervalo de temperaturas
estudiado. Sin embargo, un aumento en el contenido en agua parece proteger al producto frente a
la formaci6n de per6xidos. Ademas, este efecto resulta mas importante durante la segunda etapa
de la oxidaci6n.
’

Palabras c1ave: café, cinética, oxidación, lipidos

’

INTRODUCTION oxygen pressure are decisive in the oxidation velocity

During storage roasted coffee looses the aroma and
flavour of ’fresh coffee’ due to some lipid oxidation
and to the degradation of some compounds inherent
to the typical aroma (Radtke, 1979; Clarke, 1986).
Factors such as temperature, relative humidity and
in roasted coffee (Ernst 1979; Clinton, 1980; Baesso et
al., 1990; Hinman, 1992); permeable packed coffee,
stored at 20 °C, deteriorates six to seven times faster
than vacuum packed coffee (Ernst, 1979). Moreover,
increasing the storage temperature from 20 to 40 °C
results in a three- to four-fold increase in speed of dete-
rioration (Ernst, 1979). Baesso et al. (1990) showed that
the most important factor in deterioration was the spe-
cific surface of the product exposed to the 02 in air.
The moisture content of coffee appears to deter-
mine the intensity at which the deteriorative

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68
phenomena are produced. Quast and Teixeira Neto
(1976) found that when the moisture content of
coffee increased from 4.3 to 6.3% there was a ten-fold
increase in the rate of quality change. Hardly any
data about the role of moisture content in coffee
oxidation reactions have been published. However,
the moisture level that minimizes the rancidity reac-
tions in oily products has been determined (Labuza,
1971, 1980; Koelsch et al., 1991; Karel, 1992) and this
corresponds to the monolayer moisture content.
Water molecules may impede the access of 02 to the
active sites; therefore it is very important to deter-
mine the optimal moisture level in the product
because of its influence on the deterioration reactions
and its relationship with other variables such as
temperature and oxygen pressure; this allows storage
conditions to be determined and stability to be
predicted.
The kinetics of lipid oxidationhave been described
in detail through afree radical mechanism (Labuza,
1971; Dugan, 1976; Frankel et al., 1981; Nawar, 1985;
Karel, 1986). The classical autooxidation scheme
(Karel, 1992) is commonly employed to illustrate the
molecular mechanism by which lipid oxidation is
divided into initiation, propagation and termination
steps. According to this scheme, the kinetics of lipid
oxidation can be explained through several velocity
equations in relation to the initial stage of monomol-
ecular or bimolecular hydroperoxide decomposition.
In this way, several kinetic models have been
proposed for lipid oxidation in foods, based on half
and first order (Karel, 1992) and zero and first order
(Hall, 1983) curve fitting equations. The time for the
initial stage of monomolecular hydroperoxide decom-
position-catalysed oxidation to end and the more
rapid bimolecular-catalysed phase to begin is defined
as the break point; this is generally near the threshold
point of the sensorially unacceptable product (Labuza,
1971).
The aim of this work was to study ground roasted
coffee oxidation kinetics through peroxide value con-
trol and to determine the influence of moisture
content (two levels), temperature (three levels) and
oxygen pressure (three types of packaging) on the
oxidation rate during storage.
MATERIAL AND METHODS
Materials
Ground roasted arabica coffee (Coffee arabica Linn.)
from Colombia, sieve 18, was obtained from a local
supplier.
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Methods
Sample moisture content conditioning
Samples were conditioned at two moisture levels:
(i) 26 g/kg wet basis after roasting (controlled by Karl
Fischer titration); and (ii) 43 g/kg wet basis.
Hydration was carried out at room temperature
(16-17°C) in a vacuum chamber (37 mbar) to minimize
external resistance to mass transfer and oxidation
process. The a~,, (0.753) was created by a saturated NaCI
solution. Moisture content of the samples was con-
trolled in triplicate (as described later) until the desired
value was achieved. N, was used to restore atmos-
pheric pressure in the chamber before each control.
Experimental design
Coffee samples (150 g) at two different moisture
levels, were packed in polyester-Al-polyethylene
laminate bags. Two different packaging conditions
were considered: non-sealed bags (i) under vacuum
(35 mbar) and (ii) under C02 atmosphere (packing
machine first applied vacuum to 35 mbar and then
CO, was flushed to atmospheric pressure). Packaged
samples were stored at 5, 25 and 35°C.
-
~. B-
.
Analytical determinations
The determination of moisture content was made by
Karl Fischer’s titration. The method is based on the
reflux extraction of water contained in approximately
1 g ground coffee with 50 ml of boiling methanol
during 30 min (Scholz, 1988). During the extraction,
moisture content in the sample was determined volu-
metrically, with a Karl Fischer DL-18 Metler equip-
ment.
Sample peroxide value was determined in the lipid
fraction over a period of 12 months at regular intervals
of 30 days. Lipid extraction was carried out according
to the method recommended by Folstar et al. (1975) for
isolation in green coffee beans. Thirty grams of roast
ground coffee were extracted with petroleum ether in
a Soxhlet (4 h). The solution was stored overnight in
the refrigerator, whereupon crystallized caffeine was
filtered. Anhydrous sodium sulphate was added to the
solution for 24 h to absorb its moisture content. The
solution was filtered again and solvent-evaporated by
means of a rotavapor. Inert gas (N2) was used for
restoration of atmospheric pressure.
Rancidity was determined through peroxide value
(PV) measurements according to AOAC (1980). The
analysis was carried out on samples of about 1 g
of coffee fat matter. Data are expressed as mole
equivalents of peroxides per kg of fat matter. Each
analysis was performed in triplicate.
 69
&dquo;

RESULTS AND DISCUSSION

All the storage variables - time, temperature, oxygen
and CO2 pressure and sample moisture - had a
content-significant influence (a < 0.01), on PV levels
of the coffee. All samples showed an increase in PV
throughout the storage time, depending on packaging
conditions (Figures 1 and 2). Even samples stored
under vacuum, with low oxygen pressure, show lipid
oxidation, probably because of the initial presence of
free radicals in coffee; the roasting process promotes
free radical formation associated with pyrolysis reac-
tions (Baesso et al., 1990; Morrice et al., 1993).
Sigmoidal kinetic curves were obtained in all cases.
This indicates a two step oxidation process, more or
less coupled, depending on the storage conditions.
During the first months, PV increases and reaches a
plateau between 3 and 5 months. From this point, the
oxidation rate increases sharply and the samples
achieve a high PV level at 12 months of storage in all
cases.
The classical molecular model for lipid oxidation
(Karel, 1992) establishes that reactions occur through
a chain mechanism controlled by free radical forma-
tion, with three typical steps: initiation, propagation,
and termination. The main factor affecting the reac-
tion rate was the kind of initiation reaction. On the
basis of the described reaction model, a monomolec-
ular or bimolecular reaction can be responsible for the
initiation step of the oxidative chain in coffee, through
hydroperoxide decomposition; it depends on the
initial concentration of these compounds, as observed
in other products (Koelsch et al., 1991). So, during the
first months, the initially low hydroperoxide concen-
tration favours the monomolecular initiation and,
when a critical value is attained, in line with the reac-
tion progress, the bimolecular mechanism becomes
more controlled. According to this hypothesis, the

integrated equation for the reaction rate in each stage

will be:
Monomolecular decomposition

PV1/2 = PVÓ/2 + 2 Kat 0~t< tb (1)

Bimolecular decomposition Figure 1. Peroxide value change in ground coffee

samples with a moisture content of 26 g/kg (wet weight
Kb (t -t~ basis), stored at different temperatures. (a) Under
PV = PV¡l tb ~ t (2) vacuum. (b) Exposed to the air. (c) Under C02 atmos-
where: phere.
PV peroxide value (mole equivalents/kg fat matter)
=
1. Evoluci6n del indice de per6xidos en mues-
Figura
at time t; PVo peroxide value (mole equivalents/ kg
=
tras con un contenido en humedad de 26 g/kg (base
fat matter) at time 0; PVb = peroxide value (mole homeda), almacenadas a distinta temperatura. (a)
equivalents/kg fat matter) at time tb; Ka and Kb rate =
Muestras a vacio. (b) Muestras no selladas. (c) Muestras
constants; tb break point.
=
con C02-

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70

Equations (1) and (2) were fitted to the experi-

mental results for each storage condition by means of
a linear regression procedure. The break point for the

beginning of bimolecular control was taken at the

inflexion point of the curves (Figures 1 and 2), whose
PV corresponds to the plateau ordinate (PVb). PV~
values (Tables 1 and 2) depend on the storage temper-
ature in samples with low moisture content, but are
almost temperature independent in hydrated
samples. It is remarkable that both temperature and
product moisture content seem to affect the critical
level of hydroperoxides where the bimolecular mech-
anism controls the overall reaction rate.
Predicted PV from the fitted model versus the
experimental values of samples with two different
moisture levels (r’-, 0.960 and 0.978, respectively)
showed that the model fits hydrated samples data
better probably because of a higher homogeneity in
the moisture content (Figure 3)
The Ka values were affected by the levels of the
storage variables, increasing when the temperature
rose (Tables 1 and 2). Despite the same level of oxygen

pressure in vacuum- and CO,-packaged bags, very

Figure 2. Peroxide value change in ground coffee
samples with a moisture content of 43 g/kg (wet weight
basis), stored at different temperatures. (a) Under
vacuum. (b) Exposed to the air. (c) Under CO2 atmos-
phere.
Figura 2. Evoluc16n del indice de per6xidos en mues-
tras con un contenido en humedad de 43 g/kg (base
h6meda) almacenadas a distinta temperatura. (a)
Muestras a vacio. (b) Muestras no selladas. (c) Muestras
con CO, .
different Kg values were found in each case.
Furthermore, it is remarkable that at 35 °C very close
Ka values were obtained for the different storage
conditions; hydrated samples had the minimum
values. From the data in Table 1, it is evident that the
Arrhenius equation did not fit adequately the temper-
ature influence on Ka behaviour. Sudden jumps of Ka
occurred within the temperature range analysed in
almost all the cases. These took place between 25 and
35 °C for samples packed under vacuum conditions
and low water content and between 5 and 25 °C for
hydrated vacuum packaged samples and low mois-
ture samples packaged with C02 and not sealed.
These two last packaging methods in hydrated
samples lead to small changes in Ka due to tempera-
ture increases. The evolution of Ka in line with
temperature seems to imply a strong reactant mobility
change at a critical temperature inside the studied
range that could be attributed to a phase-transition
temperature. A calorimetric or thermomechanical
study is needed to confirm this.
Two aspects need to be considered before
explaining the last results. First, the progressive
hydration of samples stored in non-sealed bags,
caused by the hygroscopic properties of coffee (Ortold
et aL, 1993) and the high ambient relative humidity
(about 70%). Secondly, the apparent C02 adsorption
by coffee particles; after being packed, bags with C02
appeared strongly compacted, as if vacuum packed.
This fact indicated that the initial C02 gas became an

adsorbed component (as previously described

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 71

Table 1. Kinetic rate constants obtained for each of the monomolecular and biomolecular stages of lipid oxida-
tion in samples with a moisture content of 26 g/kg (wet weight basis).

Tabla 1. Valores de las constantes cindticas en los ajustes de los dos tramos de las curvas, en muestras alma-
cenadas con una humedad de 2,6% (b.h.).

Table 2. Kinetic rate constants obtained for each of the monomolecular and biomolecular stages of lipid oxidation
in samples with a moisture content of 43 g/kg (wet weight basis). ,

- .. ’,
Tabla 2. Valores de las constantes cinéticas en los ajustes de los dos tramos de las curvas de muestras almace-
nadas con una humedad de 43 g/kg (b.s.).

(Mitsuda et al., 1973), which could act like a compat-
ible liquid for some of the coffee compounds,
contributing to its molecular mobility.
The plasticizing effect of water or C02 on solid
coffee compounds could be responsible for the
different Kg evolution with temperature under each
of the storage conditions. The levels of water or
adsorbed C02 in the samples seems to change
abruptly the mobility of the reactant solids within the
considered temperature range, giving very different
reaction rates. Figure 4 shows a hypothetical evolu-
tion of the critical temperature (T,) of this change
for the solids, depending on the degree of plasti-
fication (related to the level of water content or
adsorbed CO2), The vertical trajectory in the diagram
at plastification levels 1, 2 and 3 could show the
representative point of the product at the three
storage temperatures. Strong changes in mobility and

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72

Figure 4. Hypothetical evolution of the critical temper-

ature (Tc) for solids mobility change depending on the
degree of plastification.

Figura 4. Evoluci6n hipot6tica de la temperatura

critica (Tc) de cambio en la movilidad de los reactivos
en funci6n del grado de plastificaci6n.

Despite the plasticizing role of water a protective

Figure 3. Predicted peroxide values derived from
quadratic and exponential fitting model vs observed
peroxide values. (a) Moisture content 26 g/kg (wet
weight basis). (b) Moisture content 43 g/kg (wet weight
basis).
Figura 3. Valores predichos del indice de per6xidos
segun el modelo lineal y exponencial frente a los
valores experimentales. (a) Humedad 26 g /kg (b.h.). (b)
Humedad 43 g/ kg (b.h.).
effect was also detected in some cases. It is seen, at
35 °C in vacuum-stored samples, that the Kg is lower
when the water content increases; a similar situation
was found for samples in non-sealed bags at 25 and
35 °C. These facts seem to indicate that when the
reacting mobility was increased above a critical level
water uptake diminishes the peroxides formation rate.
Probably, a solvatation effect on free radicals
contributes to this decrease in reactivity.
In the second stage of the oxidation process, where
a bimolecular mechanism controls the overall reaction
rate, the protective role of water was observed in all
cases; the maximum PV attained at 12 months of
storage was always inferior for hydrated samples,
when comparing the same storage conditions. We can
observe the lower influence of the storage variables
on the rate constant in this period. Even a decrease

reactivity occur in when temperature over-

samples
comes the
Tc That
curve. occurs between 25 and 35 °C
at plastification level 1, between 5 and 25 °C for level
2 and does not occur in the studied temperature range
for samples with level 3. According to this, water and
C02 contents sample VI could be in the level named
1, samples Al, Cl and V2 in the level named 2 and
samples A2 and C2 in the level named 3, which agree
with the Ka sequence. Samples in non-sealed bags
have a higher plastification level than expected
because of their progressive hydration, as mentioned
’
of Kb (Tables 1 and 2) in line with temperature
increase was detected. However a mathematical
effect, due to the non-determination of tbl could affect
Kb values. Moreover the few experimental points at
this stage make mathematical analysis difficult.
CONCLUSIONS
From the results obtained we can conclude that water
or other plasticizing agents and temperature affect the
kinetic oxidation of ground coffee interactively. The

above. deterioration process becomes slower when the react-

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ing mobility is decreased below a critical level (low
moisture or content and temperature).
plasticizer
Nevertheless, increase in water content seems to exert
a protective role as to the effect of oxidation
opposed
reactions. The level of oxygen pressure in the studied
range appears to play a secondary role in the deterio-
ration process.
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