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q Institution of Chemical Engineers

KINETICS OF ASCORBIC ACID DEGRADATION AND

NON-ENZYMIC BROWNING IN POTATOES
W. A. M. MCMINN (GRADUATE) and T. R. A. MAGEE (MEMBER)
Department of Chemical Engineering, The Queen’ s University of Belfast, Belfast, Northern Ireland

T
he desire to maximize product quality during drying places constraints on any chosen
dryer/drying operation. The quality attributes of dehydrated potato samples (Solanum
tuberosum) were investigated with regard to the two indices of deterioration namely,
ascorbic acid retention and non-enzymic browning. High performance liquid chromatography
was employed to evaluate the ascorbic acid loss quantitatively, while a colourimetric technique
was adopted to assess the progression of the non-enzymic browning reaction. The ascorbic acid
deterioration and non-enzymic browning reactions demonstrated ® rst- and zero-order kinetic
behaviour, respectively, and further presented a moisture content- and temperature- dependence.
The latter dependence conformed to the Arrhenius correlation.
Keywords: Arrhenius relation; ascorbic acid degradation; convective drying; moisture
content; non-enzymic browning; potato cylinders

INTRODUCTION methods. This represents a simple, rapid, highly selective

During any drying operation, one critical entity, competing
with that of process economics, is quality preservation.
Although most dehydrated fruits and vegetables are
generally produced by hot air dehydration, conventionally
air dried products tend to exhibit indifferent quality
attributes, due to excessive thermal damage and structural
changes in the product. With this in mind, this work will
focus on the variation in quality attributes of dehydrated
potato samples. Due to the complex nature of food products
and the wide range of temperatures and moisture contents
developed within the system, the quantitative description of
the relations between the processing conditions and product
quality has proved dif® cult1 . With respect to the drying
process, quality deterioration mechanisms may be classi® ed
as nutritional, chemical or physical, as summarized in
Table 12 .
From a nutritional perspective, the extent of ascorbic acid
or vitamin C retention is a widely adopted quality criterion.
The selection of ascorbic acid as a test nutrient is not
arbitrary, as its high temperature- and moisture- sensitivity
renders it indicative of the mildness of the drying process3,4 .
Numerous pathways for ascorbic acid degradation have
been postulated, however, irrespective of the exact nature of
the complex reaction mechanism, destruction of this heat
liable nutrient may be represented in a simpli® ed form5 :
Ascorbic Acid (AA) $ Dehydroascorbic Acid
(DHAA) ! Products
Numerous techniques have been employed to monitor
ascorbic acid activity. Although chemical estimation is still
widely adopted, practical limitations, such as the presence
of interfering compounds in the complex food matrix, have
resulted in the replacement of traditional approaches
with high-performance liquid chromatographic (HPLC)
223
and sensitive technique6 . On consideration of available
HPLC methods, an ion-exclusion chromatographic separa-
tion technique was used here, as recommended by Graham
and Annette7 .
Without exception, the drying of foodstuffs has been
demonstrated to have a negative effect on the stability of
ascorbic acid. The degradation reaction characteristically
exhibits(pseudo-) ® rst-order kineticbehaviour,with examples
reported in the literature for many systems, e.g. simu-
lated cereal food systems5 , cellulose model systems3 ,8 and
potatoes9 ,1 0 . However, the ® rst-order rate constants exhibit
system speci® city5 .
Researchers have further acknowledged the temperature-
dependence of the reaction. In general, the temperature
sensitivity is manifested by a progressive increase in
ascorbic acid loss with increasing temperature, and thus,
interpretation is realized on application of the Arrhenius
correlation to the ® rst-order rate constant3 ± 5 ,8 ,1 0 . Subse-
quent evaluation of the activation energy for the reaction
facilitates a further understanding of the degradation
mechanism1 1 . However, despite a degree of moisture-
dependence, divergent functional forms have been reported
by several researchers1 1 . Kirk et al.5 , and Lee and Labuza8
observed no signi® cant variation in the activation energies
characterizing model food systems, while Mishkin adopted
a third order polynomial to correlate the activation energy
enhancement within dehydrated potato samples4 ,1 0 .
The moisture dependent nature of the reaction has also
been recognized by many authors. Preliminary studies
conducted by Lee and Labuza8 , within an intermediate
moisture content range, indicated a progressive increase in
the reaction rate with increasing moisture content5 ,8 , in an
attempt to interpret this increase in destruction rate, the
authors proposed the concept of decreased reactant viscosity
and, hence, enhanced mobility (diffusion) at high moisture
contents. In direct contravention, the work of Villota and
224 MCMINN and MAGEE
Table 1. Quality considerations during drying of food systems2 .
Nutritional Chemical Physical
Vitamin loss Browning reactions Rehydration
Protein loss Lipid oxidation Solubility
Microbiological quality Colour loss Texture
Aroma/¯ avour loss
Karel3 , and Mishkin et al.4 ,1 0 revealed a slowing down of
the reaction at high moisture contents. The former authors
ascribed this behaviour to the existence of dilution effects,
while the latter recognized the contribution of the variant
physical phenomena within the system. The reaction was
further characterized by a maximum degradation rate at a
product and/or process speci® c moisture level. In particular,
a `critical’ moisture content value of 2±2.5 kg/kg dry solid
was associated with ascorbic acid degradation during the air
drying of potato samples. A reduction in the rate of ascorbic
acid loss was also evident within the low moisture content
range. This was considered to re¯ ect a restriction in the
mobility of the reactant species3 .
Quantitative representation of kinetic data has also been
extensively reported in an attempt to predict and optimize
ascorbic acid retention during drying and storage. Conse-
quently, many authors have proposed mathematical models
and computer simulations representing ascorbic acid con-
centration as a function of moisture content, temperature and
time3 ,9 ,1 0 . Mishkin et al. explored the optimization of potato
air drying with respect to product quality. Accordingly, the
authors postulated an optimal operating policy for maximiza-
tion of ascorbic acid retention, namely employment of
reduced operating temperatures at the onset of processing,
followed by temperature elevation as the drying proceeds,
and the ascorbic acid becomes more stable1 0 .
Further characterization of the thermal damage incurred
during drying may be realized in terms of the development
of non-enzymic browning1 . Although this dominant deterio-
rative reaction may occur via three pathways, researchers
have recognized the primary importance of the Maillard
reaction with respect to food processing. This mode of
deterioration constitutes a diverse group of reactions
between amino groups and active carbonyl groups, leading
eventually to the formation of insoluble, polymeric
pigments, collectively known as melanoidin pigments1 2 .
For the most part, the non-enzymic browning reaction is
considered undesirable, with the browning compounds
contributing to the development of quality characteristics
such as off-¯ avours, undesirable colour, decreased solubility,
decreased nutritional value, textural changes, destruction of
vitamins and increased acidity. Therefore, in an attempt to
redress this deleterious reaction, researchers have assessed
the effectiveness of various treatments for non-enzymic
browning inhibition. At present, sulphite pretreatment is
recognized as the only practical and effective means for
controlling non-enzymic browning in dried fruit and
vegetable products1 2 .
Extensive investigations with regard to the non-enzymic
browning reaction in food systems have revealed several
characteristic features. The progression of the reaction is
primarily characterized by an initial, moisture- and
temperature- dependent induction period, during which the
extent of pigment formation is not appreciable1 ,3 ,1 3 ± 1 8 .
Moreover, Labuza et al. regarded this as an inductive stage,
wherein the induced chemical changes resulted in the
formation of colourless and tasteless browning intermedi-
ates1 9 . However, the limited signi® cance of this lag time has
become apparent. Rather, the post-lag period is of primary
importance in dictating the ® nal quality of the system1 . With
this in mind, researchers have characterized the develop-
ment of non-enzymic browning in numerous food systems
namely, vegetables1 3 ,1 8 ,2 0 , fruits1 6 , model food systems1 4 ,1 7 ,
and milk products1 ,1 5 . In general, the index of browning
increases linearly with time, and thus, may be considered to
conform to (pseudo-) zero-order kinetic behaviour.
Supplementary characterization of the degradation reac-
tion revealed a further dependence on the parameters of
temperature and moisture content2 . Typically, the reaction
rate increases with temperature according to the Arrhenius
relationship, with the degree of temperature sensitivity
exhibiting predominance at low moisture contents1 8 ,2 0 . This
was manifested by an inversely proportional relation between
activation energy and moisture content. However, the variant
functional forms of the activation energy versus moisture
content correlations re¯ ect a degree of system speci® city.
Mizrahi et al. proposed an exponential relation to evaluate the
experimental data of dehydrated cabbage1 3 ; Mishkin et al.
adopted a linear correlation for potatoes2 1 ; a third degree
polynomial was assumed for grapefruit samples1 6 , and an
empirical correlation described the experimental data of
milk1 .
Numerous studies have also been conducted to address
the complex moisture-dependent characteristics of the non-
enzymic browning reaction. Labuza et al. demonstrated the
existence of a maximal reaction rate, accompanied by a
decrease in rate at both low and high moisture contents.
Accordingly, the authors ascribed this behaviour to the state
or boundness of water, and the mobility of the reactant
species. At low moisture contents, the decrease in reaction
rate was correlated with the diffusional limitations of the
reactants in the highly viscous matrix. However, above the
critical moisture content, the `mobility-dilution’ theory
acknowledged the predominance of dilution effects and the
reaction inhibition by water1 9 . This is one of the reaction
products1 5 . The theory of Labuza et al. was employed by
Rapusas and Driscoll to interpret the quadratic moisture-
dependence of the non-enzymic browning reaction in white
onion slices1 8 . Hendel et al.2 0 , and Franzen et al.1 also
observed the presence of maximum browning rates at 15%
moisture (dry basis) and at 7% moisture (dry basis) in potato
and milk samples, respectively. Accordingly, Franzen et al.
attributed the dissimilar moisture contents to the composi-
tional differences of the materials1 . Moreover, Troller
reported typical `browning-critical moisture contents’ for
dehydrated food systems within the water activity range
0.65 to 0.752 2 .
In a complementary investigation, Hendel et al. explored
the progression of the browning reaction during the drying
of potato samples. The authors reported more severe quality
deterioration at low moisture contents, and thus, proposed
that the maximum browning rate was, in fact, associated
with the latter stages of processing. This is in direct
contravention to investigations performed under conditions
of constant moisture content, wherein the presence of a
reaction maxima was observed at an intermediate moisture
content. The authors further recognized that during drying
Trans IChemE, Vol 75, Part C, December 1997
 KINETICS OF ASCORBIC ACID DEGRADATION AND NON-ENZYMIC BROWNING IN POTATOES
the time interval associated with the `browning-critical
moisture content’ was of minor signi® cance2 0 .
In view of the unlimited number of food formulations,
several product speci® c correlations have been developed to
characterize non-enzymic browning. Each model presents a
similar mathematical form, with the temperature depen-
dence interpreted in terms of the Arrhenius relation, and the
in¯ uence of moisture content re¯ ected in the correlation
coef® cients1 ,1 3 ,1 6 ,1 8 ,2 1 .
Researchers have undoubtedly acknowledged the increas-
ing emphasis which consumers place on nutritional and
chemical quality. However, despite the progress with regard
to reaction characterization and due to the delicate character
of biological products and the demand for superior quality
attributes, it is evident that all aspects of quality preserva-
tion will continue to remain at the forefront of drying
research.
MATERIALS AND METHODS
Procedure
The drying experiments were performed in the experi-
mental air tunnel dryer according to the procedure
previously detailed2 3 . The ascorbic acid retention and non-
enzymic browning reactions were evaluated as a function of
moisture content. Therefore, the cylindrical potato samples
(initial radius 13.5 mm and length-to-radial ratio 4 : 1) were
predried (in a vertical orientation undergoing radial
diffusion) to the appropriate moisture content, ranging
from fresh (4.6 kg/kg dry solid) to 0.5 kg/kg dry solid, in
increments of approximately 0.25 kg/kg dry solid. Air
temperatures of 30, 45 and 608 C and ¯ owing at a velocity
of 1.5 ms- 1 were adopted, with previously established
drying curves facilitating determination of the drying
time23 . For assessment of product quality the samples
were not subjected to SO2 pretreatment. However, to
evaluate the degree of non-enzymic browning, the samples
were preblanched to eliminate enzymatic browning. Each
experimental run was performed in triplicate and the
corresponding quality measurements averaged.
Blanching
The samples for water blanching were tightly wrapped in
moisture-proof material and immersed in boiling water for
nine minutes to inactivate the enzymes. Following treat-
ment, the samples were rinsed with distilled water to remove
surface gelatinized starch, and then further cooled in ice-
water to stop the reaction. Surface moisture was then
adsorbed with ® lter paper.
A representative duplicate sample was also tested for
peroxidase deactivation by the standard peroxide-guaiacol
method. Peroxidase is one of the most heat-stable enzymes
in plants and this represents the recognized criterion by
which the effectiveness of the blanching process is assessed.
This assay involved ¯ ooding the surface of the sample with
0.05% solutions of guaiacol and hydrogen peroxide (BDH,
Poole, UK). Accordingly, the available peroxidase reacts
with the solutions to produce a reddish-brown colouration.
However, the portion of the surface which remains colour-
less is indicative of enzyme inactivation2 4 . There was no
attempt to optimize blanching time and temperature in this
study.
Trans IChemE, Vol 75, Part C, December 1997
225
Ascorbic Acid
The l-ascorbic acid (AA) contents of fresh, dried and
partially dried potato samples were determined using a high-
performance liquid chromatography (HPLC) technique. The
separation of ascorbic acid was achieved using a Shimadzu
liquid chromatograph equipped with an ultraviolet-visible
photodiode-array detector (Model SPD M10A), an auto-
matic sample injector (SIL-10A) and a communications bus
module (Model CBM-10A). It was further connected to a
DELL 466I computer installed with Class LC10 software
(Mason Technology, Ireland). The system employed a Bio-
Rad Aminex HPX-87H, 300 mm ´ 7.8 mm internal diameter
ion-exclusion column. This was packed with sulphonated
styrene-divinylbenzene copolymer resin (8% cross-linked
and particle size 9 l m), and was installed with a Micro-
Guard cation H+ cartridge to maintain the performance and
prolong the lifetime of the analytical column (Bio-Rad
Labs, Hemel Hempstead, UK). The column was maintained
at an ambient temperature of 22 6 28 C and at a back
pressure of 90 6 1 bar, and the ef¯ uents were monitored at a
wavelength of 245 nm. The analysis time was approxi-
mately twenty minutes, which included a post column
elution period of ® ve minutes.
The samples were prepared for analysis according to the
procedure proposed by Graham and Annette7 . A 30 g potato
sample was blended with 80 g of 62.5 mM metphosphoric
acid in a Waring blender for 3 minutes. Due to problems
caused by frothing, mass rather than volume adjustments
were made, with metaphosphoric acid solution being added
to adjust the weight of the homogenate and washings to
150 g. The mixture was then centrifuged at 6500 g for 15
minutes and ® ltered. An aliquot of ® ltrate (a volume such
that the ascorbic acid concentration was between 5 and
20 l g ml- 1 ) was diluted to 20 ml with 62.5 mM metaphos-
phoric acid and the sample extracts stored at 58 C. 20 l l
samples of extract was then injected into the HPLC system
and eluted with 4.5 mM sulphuric acid at a ¯ owrate of
0.6 ml min ± 1 .
In addition to ascorbic acid, vitamin C also occurs in its
oxidized form as l-dehydroascorbic acid (DHAA). As a
proportion of the ascorbic acid may be oxidized during
drying, analysis for vitamin C activity must take this into
consideration. The dehydroascorbic acid content was
evaluated on the basis of the difference between the total
ascorbic acid after dehydroascorbic reduction and the
ascorbic acid content of the original sample.
The reduction of dehydroascorbic acid to ascorbic acid
was accomplished using a minor modi® cation of the method
proposed by Hughes et al.2 5 . This involved addition of
0.5 ml of 30 mM dl-homocysteine solution (Sigma, Poole,
Dorset, UK) to 3 ml of the extract, followed by a pH
adjustment to 6.8±7.0 by slow addition of 1.5 ml of 2.6 M
dipotassium hydrogenphosphate (Sigma, Poole, Dorset,
UK). Then, after thirty minutes, the reaction was stopped
by addition of 1 ml of 62.5 M metaphosphoric acid.
To enable a standard ascorbic acid curve to be
established, 20 l l aliquots of a standard solution of ascorbic
acid were analysed. These standard solutions were freshly
prepared by diluting a stock solution of ascorbic acid to the
appropriate concentration with 62.5 mM metaphosphoric
acid. The stock solution (200 l g ml- 1 ) was prepared by
dissolving 20 mg of ascorbic acid (Sigma, Poole, UK) in
226 MCMINN and MAGEE
100 ml of 62.5 mM metaphosphoric acid (BDH, Poole, UK).
Without exception the analytical solutions, including the
4.5 mM sulphuric acid mobile phase, were prepared with
high purity water obtained using an Elgastat Option 3 water
puri® er (Elga, High Wycombe, UK).
Under the experimental chromatographic conditions,
ascorbic acid was eluted after a period of 10.0 6 0.20
minutes. In addition to the predominant peak associated
with ascorbic acid, the chromatograms of the potato samples
typically exhibit secondary peaks. This behaviour may be
attributed to the presence of co-extracted material although
it is recognized that their existence does not interfere with
the separation of ascorbic acid7 .
Non-Enzymic Browning
The degree of non-enzymic browning was determined
according to the procedure proposed by Hendel et al.2 0 . This
colourimetric technique is based on the variation in 55%
ethanol-extracted colour, detected at 390 nm.
Initially, the potato sample was ground using a laboratory
hammer mill. A 10 g sample was then extracted with 200 ml
of 55% ethanol (BDH, Poole, UK) and the contents of the
¯ ask mechanically agitated for two hours. The colour is
stable for several hours in darkness, but fading has been
observed for extracts exposed to sunlight. With this in mind,
the ¯ asks were wrapped in dark paper whilst being shaken.
Following agitation, the extract was ® ltered through What-
man No. 3 ® lter paper, ensuring the funnel was covered to
prevent solvent evaporation. An aliquot of the ® ltrate was
placed in a 1 cm glass curvette (4 ml volume) and the
absorbance measured at 390 nm in an ATI Unicam, Model
8625 ultraviolet-visible spectrophotometer with a 1cm path
length (Wishart Scienti® c Ltd, UK). Deionized water was
used as a reference sample. The absorbance was expressed
in terms of the absorbance.
RESULTS AND DISCUSSION
Ascorbic Acid
In common with most research concerning the deteriora-
tion of nutritional quality during food processing, ascorbic
acid or vitamin C was chosen as a test nutrient. This is
regarded as a non-subjective, relatively easy-to-measure
criterion of food quality11 . Within the complex matrix of the
raw potato, ascorbic acid may exist in two biologically
active forms, namely l-ascorbic acid (AA) and l-dehydro-
ascorbic acid (DHAA). Therefore, as a proportion of the
ascorbic acid may be oxidized during the drying process,
determination of the sample’ s total ascorbic acid content
(TAA) was achieved on the basis of a summation of both the
ascorbic acid and dehydroascorbic acid contents. The
average ascorbic acid content of the raw potato samples
was 14.5 6 0.24 mg/100 g- 1 fresh weight, with the dehy-
droascorbic acid typically retaining from 35 to 50% of the
vitamin activity. However, it must be stressed that the
values are highly dependent on factors such as cultivar,
conditions during growth and degree of maturity.
Figure 1 illustrates the experimental and predicted
ascorbic acid degradation characteristics of potato samples.
Development of the predicted values will be outlined in the
following discussion. It is clear that irrespective of the air
drying temperature, the removal of moisture is accompanied
by a progressive decrease in the ascorbic acid concentration.
Figure 1. Total ascorbic acid retention (CTAA)* characteristics of dried
potato samples. *(CTAA represents the concentration normalized with
respect to the initial concentration).
Furthermore, the deterioration characteristics exhibit a
temperature dependence, as demonstrated by the lower
ascorbic acid concentrations in samples dried at an elevated
temperature, i.e. 608 C. To facilitate interpretation of the
kinetic behaviour, the classical isothermal kinetic approach
was adopted. This involves analysis of ascorbic acid
retention as a function of time, at a constant temperature.
The results of the evaluation indicate the presence of a ® rst-
order reaction. Thus, the degradation characteristics may be
further expressed by the following mathematical expression:
d[CTAA ]
dt = - TAA TAA
k [C ] (1)
where CT A A is the concentration of ascorbic acid (normal-
ized with respect to initial concentration); t the time (min),
and kT A A the ® rst-order rate constant (min- 1 ).
The presence of ® rst-order reaction kinetics was con-
® rmed by graphical interpretation of the integral of equation
(1). In accordance with the mathematical expression, the
experimental ln[CT A A ] versus time curve exhibited a linear
correlation, with a slope equivalent to the rate constant,
kT A A . Application of the analysis to the experimental data
corroborated the existence of ® rst-order kinetic behaviour.
The predicted ® rst-order characteristics are demonstrated in
Figure 1.
The ascorbic acid degradation may be alternatively
represented by the equation:
[CTAA ] = [C0 ] exp(-kTAA t) (2)
where C0 is the normalized value of the initial ascorbic acid
concentration, i.e. C0 = 1.
Supplementary quantitative analysis of the ascorbic acid
degradation data was realized on evaluation of the reaction
constants, kT A A . The characteristic parameters were estab-
lished by ® tting the experimental data to the empirical
model represented by equation (2). The capacity of this
model to represent the experimental data was realized in
terms of the mean relative percentage deviation modulus, E,
as de® ned by equation (3):
100 N
| ei - pi |
E% = (3)
N i=1
ei
where ei and pi are the experimental and predicted values,
respectively, and N the number of experimental observations.
Trans IChemE, Vol 75, Part C, December 1997
 KINETICS OF ASCORBIC ACID DEGRADATION AND NON-ENZYMIC BROWNING IN POTATOES
Table 2. Ascorbic acid degradation characteristics.
Air temperature ( 8 C) 30
C0 0.988
kTAA (´ 10- 3 min- 1 ) 0.4
r2 0.959
E (%) 2.47
Logarithmic relation CTAA = 0.299 ln X + 0.549
r2 0.946
Range of application (kg/kg dry solid) X$ 0.159
This parameter is widely adopted throughout the
literature to evaluate the goodness of ® t of mathematical
expressions, and in general moduli below 10% are
indicative of a reasonably good ® t for practical purposes.
The results of the analysis are summarized in Table 2. In
keeping with the experimental results presented in Figure 1,
the estimated rate constants indicate a concurrent increase
in the reaction rate with increasing drying temperature.
Thus, the resultant decrease in ascorbic acid retention
corroborates the heat labile character of the nutrient. The
observations are in accordance with those of other
researchers, who also adopted ® rst-order reaction kinetics
to describe ascorbic acid degradation4 ,5 ,8 ,9 .
The foregoing analyses and discussion provide evidence
that air drying temperature is a dominant in¯ uence with
respect to the ascorbic acid degradation characteristics.
With this in mind, the temperature dependence of the
reaction was quanti® ed on the basis of the generally
accepted Arrhenius correlation:
kTAA = k0 exp[-Ea / RT ]
where k0 is the Arrhenius pre-exponential factor (min- ); Ea
the energy of activation (kJmol- 1 ); R the universal gas
constant (8.314 Jmol- 1 ), and T the temperature (K).
Accordingly, the experimental data were presented
graphically in the form: ln kT A A versus 1/T, and the
corresponding activation energy calculated from the slope
of the straight line. Furthermore, interpretation with regard
to a possible moisture content dependence was achieved by
application of the analysis at speci® c moisture contents.
Figure 2 reveals that the activation energy increases with
rising moisture content, in accordance with a third-order
polynomial relation. This behaviour re¯ ects the enhanced
Figure 2. Activation energy for ascorbic acid degradation.
Trans IChemE, Vol 75, Part C, December 1997
227
45 60
0.998 0.990
0.6 0.7
0.969 0.981
3.63 1.89
CTAA = 0.269 ln X + 0.609 CTAA = 0.282 ln X + 0.567
0.968 0.977
X$ 0.104 X$ 0.134
energy requirements to induce ascorbic acid destruction at
high moisture contents. An Arrhenius expression exhibiting
a comparable functional form was also reported by Mishkin
et al.4 ,1 0 .
The discussion to date reveals that processing time and
temperature are the predominant factors with respect to the
degradation behaviour. However, the inter-related para-
meter of sample moisture content may also be instrumental
in dictating the reaction characteristics. Graphical repre-
sentation of the experimental ascorbic acid concentration as
a function of moisture content is presented in Figure 3. The
moisture content dependence of ascorbic acid deterioration
is manifested in the form of a logarithmic decay and Table 2
details the results of the regression analysis. However, the
mathematical nature of the function allows for prediction
only within the speci® ed moisture content range.
The variation in ascorbic acid concentration with respect
to moisture content may be the result of several contributory
factors. The concept of `dilution effects’ , postulated Villota
and Karel3 may, in part, provide an explanation for the
(4)
observed behaviour. Primarily, the samples present high
1
moisture contents, which in turn lowers the ascorbic acid
concentration, thereby inducing a relatively slower reaction
rate. However, supplementary to this chemical phenom-
enon, the physical structure of the potato may also be
instrumental in rendering the initially low rate of ascorbic
acid loss. During the early stages of drying, the tissue would
appear to retain a high degree of membrane integrity, and
thus impart a degree of protection from deleterious cell
components. However, as drying proceeds cellular com-
partmentation will be lost which induces accelerated
reaction kinetics and, hence, enhanced ascorbic acid
degradation. Furthermore, Mishkin et al. elucidated the
Figure 3. Ascorbic acid retention as a function of moisture content.
228
slow initial reaction rate to the presence of endogenous
antioxidative constituents1 0 .
The degradation characteristics are comparable with the
observations reported by Mishkin et al.1 0 , and Villota and
Karel3 . However, the complexity of plant tissue together
with varying preprocessing histories and the system-
dependent nature of the reaction, rendered slight variations
in the kinetic data, i.e. the current research does not exhibit a
maximum degradation rate at intermediate moisture con-
tents.
During drying of the potato samples, one important
performance function is optimization of ascorbic acid
retention. However, due to the wide range of temperatures
and moisture contents transversed by the sample during
processing, any attempt at optimization must address the
relative contribution of each system component. At high
moisture contents, elevated operating temperatures render a
slightly increased degree of degradation, as demonstrated in
Figure 4. This behaviour is indicative of the enhanced
temperature sensitivity of ascorbic acid at high moisture
contents. By adopting enhanced drying temperatures,
comparatively shorter times are required to attain low
moisture contents. As a result there is a relatively decreased
level of ascorbic acid degradation. It therefore follows that
operating conditions of 308 C require comparatively longer
times to achieve low moisture contents and as a result, lower
levels of ascorbic acid are retained. This is irrespective of
the decreased degradation rate induced by lower tempera-
tures. Thus, it may be inferred that ascorbic acid is more
adversely affected by an increased processing time than an
elevated processing temperature. In view of the foregoing
discussion, the objective of process optimization may be
attained by selecting a favourable combination of tempera-
ture and time, e.g. operating at a low temperature during the
early phases of drying, followed by temperature elevation as
the moisture content falls. Alternatively, under constant
processing conditions, an intermediate air temperature of
458 C would also render a comparable, if not higher, degree
of ascorbic acid.
Non-Enzymic Browning
Non-enzymic browning is a quality attribute of primary
importance in many dehydrated food systems. However, it
Figure 4. Degradation of total ascorbic acid as a function of air temperature
and moisture content.
MCMINN and MAGEE
Figure 5. Non-enzymic browning in potato samples during drying at
different air temperatures.
is the widely acknowledged that the mechanism associated
with the production of such undesirable, dark coloured
products constitutes a complex series of reactions. Figure 5
illustrates the progression of the non-enzymic browning
reaction during the drying of potato samples at different
air temperatures. This was quanti® ed in terms of the
absorbance of the extracted sample at 390 nm.
During the initial stages of the browning reaction, the
experimental absorbance measurements indicate a minimal
level of colour development. This introductory period is
commonly perceived as an `induction’ stage, wherein the
chemical reaction constitutes the preferential formation of
colourless browning intermediates1 . However, the beha-
viour may also, in part, re¯ ect the temperature differential
displayed between the sample and the air drying tempera-
ture. Accordingly, the lower than predicted temperature will
render a slower reaction rate. Figure 5 further illustrates the
temperature dependence of the `induction’ period, with the
high processing temperature displaying a reduced `lag’
time.
Following the production of a suf® cient quantity of the
intermediate products, the reaction proceeds to its ® nal
stage, as characterized by the formation of the brown
pigments (melanoidins). The absorbance measurements
clearly demonstrate a concurrent increase in colour develop-
ment with drying time, irrespective of the air drying
temperature. This is manifested in the form of a linear
correlation, as illustrated in Figure 5. Thus, it would appear
that the non-enzymic browning which accompanies potato
drying conforms to a zero-order kinetic reaction. This may
be represented in the form:
d[B]
dt = b
k (5)
where [B] is the concentration of brown pigment (absor-
bance); t the drying time (min), and kb the zero-order rate
constant (min- 1 ).
The degradation reaction may be alternatively represented
by the integral of equation (5):
[B] = [B0 ] + kb t (6)
where B0 is the initial absorbance.
Accordingly, the reaction constants were established
by ® tting the absorbance data to the empirical model
represented by equation (6). The results of the regression
Trans IChemE, Vol 75, Part C, December 1997
 KINETICS OF ASCORBIC ACID DEGRADATION AND NON-ENZYMIC BROWNING IN POTATOES
Figure 6. Activation energy for non-enzymic browning.
analysis are detailed in Table 2 and the corresponding
predicted equations illustrated in Figure 5. The estimated
coef® cients clearly reveal the temperature dependence of
the deterioration reaction. Furthermore, the relative magni-
tude of the parameters corroborates the earlier observations
of a progressive enhancement of the browning rate with
increasing air temperature. This is illustrated in Figure 5. A
possible explanation for this behaviour may be offered on
consideration of the reactant mobility. At the higher
temperature, the diffusional resistance within the product
matrix is lessened, and this in turn imparts a lower level of
restriction on the reaction rate. As anticipated, the dominant
in¯ uence of air drying temperature conforms to the
Arrhenius function:
kb = kb0 exp[-Ea / RT ]
where kb 0 is the Arrhenius pre-exponential factor (min- 1 ); Ea
the energy of activation (kJmol- 1 ); R the universal gas
constant (8.314 Jmol- 1 ), and T the temperature (K). The
observed reaction characteristics are in keeping with those
reported for most quality-related deterioration mechanisms,
namely zero-order kinetic behaviour and a temperature
dependence represented by the Arrhenius correlation1,18,20,21.
The energy of activation characterizing the degradation
process was evaluated by adopting the procedure outlined in
the previous section. Once again, the activation energy
exhibits a moisture content dependence, as illustrated in
Figure 6. Moreover, the progressive decrease with increas-
ing moisture content is manifested in the form of a linear
relation. This inversely proportional relationship with
respect to moisture content is indicative of the enhanced
energy requirements to facilitate colour development at low
moisture contents.
In view of the moisture content dependence displayed by
Table 3. Non-enzymic browning characteristics.
Air temperature (8 C) 30
B0 0.0092
kb (´ 10- 3 min- 1 ) 0.1
r2 0.980
Exponential relation B = 0.203 exp(-0.958X)
r2 0.978
Trans IChemE, Vol 75, Part C, December 1997
229
Figure 7. Non-enzymic browning in potato samples as a function of
moisture content.
the ascorbic acid degradation characteristics it may be
inferred that water removal will also impart a signi® cant
in¯ uence on the non-enzymic browning reaction. Evidence
to support this hypothesis is provided in Figure 7. The
results reveal that a variation in the sample moisture content
yields an exponential response with respect to colour
formation. Table 3 summarizes the results of the regression
analysis.
The non-enzymic browning reaction presents complex
characteristics with respect to the moisture content and
associated structural attributes of the system. At high
moisture contents, it would appear that several factors are
instrumental in dictating the overall reaction behaviour.
Primarily, the increased moisture content will induce
dilution of the reactant concentration, and thereby render
(7)
a retardation in colour development. Moreover, from a
chemistry perspective, the increased water presence may
impart an inhibitory effect on the condensation stages of the
reaction mechanism1 5 . The superior structural attributes of
the samples may also render a restriction in the reactant
availability. In contrast, however, Labuza et al. recognized
that a decrease in viscosity was associated with the
increased water content1 9 . Nevertheless, the experimental
results suggest that the concentration and local product
inhibition effects of water render more predominant
retardatory in¯ uences than any enhancement of the reaction
rate induced by a decrease in viscosity. As the drying
proceeds, the rate and magnitude of the colour development
becomes progressively more pronounced. This may re¯ ect
the simultaneous concentration of the dissolved reactants as
water is removed from the system. In direct contravention,
however, the `mobility-dilution’ theory suggested that an
elevated diffusional resistance and, hence, lower reaction
rate accompanied solids concentration. Therefore, assuming
45 60
0.0063 0.0029
0.2 0.3
0.972 0.980
B = 0.176 exp(-0.961X) B = 0.273 exp(-1.06X)
0.968 0.978
230 MCMINN and MAGEE
both factors are at work, the overall sample quality appears
to be primarily dictated by the former element.
Irrespective of air temperature, the lower moisture
content range represents a critical interval with respect to
quality impairment. The substantial degree of colour
formation associated with the latter stages of processing
re¯ ects the detrimental effect of prolonged drying time.
Towards the end of the drying period, removal of a small
quantity of water requires a comparatively long time. It may
be inferred that the product quality would be substantially
enhanced if the sample was dried to a slightly higher
moisture content.
Further examination of the non-enzymic browning
reaction demonstrates the absence of a `browning-critical
moisture content.’ Moreover, the interval of browning
maximum proposed by Hendel et al.2 0 , i.e. 17±20% (dry
basis), appears to impart only a minor contribution to the
overall browning response. This may be attributed to the
small inherent time interval.
Once again, Figure 7 corroborates the temperature
dependence of the deterioration reaction, with the degree
of in¯ uence imparted by the temperature parameter
appearing more predominant at low moisture contents.
Accordingly, superior quality retention may be approached
by adopting a two step drying process, wherein the majority
of the water is rapidly removed at the high temperature,
followed by lowering of the temperature within the critical
lower moisture content interval. The reported observations
further indicate that, despite the comparatively shorter
processing time, an increased degree of browning is induced
during drying at an elevated temperature. This suggests that
air temperature imparts a more predominant in¯ uence on the
degradation characteristics than processing time. However,
adopting intermediate conditions of processing temperature
and time throughout the entire drying process appears to
induce optimum quality retention.
Preliminary comparison of the degradation characteris-
tics with respect to a typical drying curve, as shown in
Figure 8, suggests that the deterioration mechanism in some
way re¯ ects generalized drying characteristics. Within a
representative curve three distinct drying periods exist,
namely a transition period (a), and two falling-rate periods
(b) and (c). The initial short (approximately 10 minutes)
`warming-up’ stage (a) corresponds to solid heating, and
consequently to non-isothermal drying conditions. With
respect to ascorbic acid degradation, the ® rst falling-rate
period (a) is characterized by a signi® cantly higher activation
Figure 8. Characteristic falling-rate drying behaviour: (a) initial transition
period; (b) ® rst falling-rate period, and (c) second falling-rate period.
energy (see Figure 2), whilst in the second falling-rate period
(b) a much reduced activation energy is observed. Moreover,
in the case of non-enzymic browning a degree of correlation
between the ® rst falling-rate period and the induction period
of the degradation is evident. This further substantiates the
signi® cance of the moisture content with respect to all aspects
of a drying operation.
CONCLUSIONS
· Ascorbic acid degradation conformed to a ® rst-order
kinetic reaction. The deterioration characteristics were
further dictated by the inter-related parameters of proces-
sing time, processing temperature and sample moisture
content.
· The non-enzymic browning reaction illustrated zero-
order kinetic behaviour. Moreover, the deteriorative reac-
tion presented a temperature- and moisture content-
dependence.
NOMENCLA TURE
[B] concentration of brown pigment, absorbance
[B0] initial absorbance
[C0] initial ascorbic acid concentration, normalized with respect to initial
concentration
[CTAA] ascorbic acid concentration, normalized with respect to initial
concentration
E mean relative deviation modulus, %
Ea energy of activation, kJmol- 1
ei experimental value
kb zero-order rate constant, min- 1
kb0 Arrhenius pre-exponential factor for non-enzymic browning reaction,
min- 1
k0 Arrhenius pre-exponential factor for ascorbic acid degradation
reaction, min- 1
kTAA ® rst-order rate constant, min- 1
N number of experimental observations
pi predicted value
R universal gas constant, 8.314 Jmol- 1
r2 coef® cient of determination
t time, s
T temperature, K
X moisture content at time, t, kg moisture/kg dry solid
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ADDRESS
Correspondence concerning this paper should be addressed to Dr W.
McMinn, Department of Chemical Engineering, The Queen’ s University of
Belfast, Belfast, BT9 5AG, Northern Ireland.
The manuscript was received 29 January 1997 and accepted for
publication after revision 17 July 1997.