FLAVOUR AND FRAGRANCE JOURNAL

Flavour Fragr. J. 2001; 16: 712

Shelf-life and mechanisms of destabilization in dilute

beverage emulsions
Roberto A. Buffo1 and Gary A. Reineccius2
1 Department
2 Department

of Food Science and Nutrition, University of Minnesota, 1334 Eckles Avenue, St. Paul, MN 55108, USA
of Food Science and Nutrition, University of Minnesota, St. Paul, MN 55108, USA

Received 21 February 2000

Revised 6 April 2000
Accepted 19 June 2000

ABSTRACT: Mechanisms of destabilization and kinetic parameters of shelf-life in dilute beverage emulsions
were investigated at six different temperatures. Close fit of the Arrhenius equation to emulsion breakage time
indicated the occurrence of similar mechanisms throughout the temperature range and validated accelerated shelflife tests at higher temperatures. Creaming increased by a factor of 10 between the lowest .4 C/ and highest
.55 C/ temperatures. Ostwald ripening was highly significant and more important than coalescence in influencing
emulsion stability. Copyright 2001 John Wiley & Sons, Ltd.
KEY WORDS: beverage emulsions; shelf-life; destabilization; kinetics

Introduction
Beverage emulsions are oil-in-water (O/W) emulsions
comprising two categories: flavour emulsions and cloud
emulsions. The former provides the beverage with flavour, cloudiness and even colour in certain formulae,
whereas the latter provides only cloudiness with no
flavour.1 A typical flavour emulsion composition includes flavour oils and weighing agents in the oil phase, and
water, hydrocolloids, citric acid, sweetener and preservatives in the water phase. Flavour oils are essential
oils, typically orange, lemon or lime. In cloud emulsions,
the flavourless oil can be orange terpenes or vegetable
oils. Hydrocolloids, typically gum arabic (gum acacia),
serve as emulsifiers and stabilizers. Modified starches or
other gums (guar, xanthan, tragacanth, locust bean or
carrageenan) can act as substitutes for gum arabic.2
Beverage emulsions are a unique class of emulsions
differing from other food emulsions in that they are
consumed in a highly diluted form rather than in their
original concentrated form. They are first prepared as an
emulsion concentrate which is later diluted several hundred times in sugar/acid solution in order to produce the
finished beverage, either carbonated or non-carbonated.1
For beverage emulsions, the most critical criterion of
stability is its stability in the finished soft drink. Emulsion stability in the concentrate is easier to achieve
because the viscosity is much higher due to the high
*Correspondence to: G. A. Reineccius, Department of Food Science
and Nutrition, University of Minnesota, 147 Food Science and Nutrition Building, 1334 Eckles Avenue, St. Paul, MN 55108, USA.
E-mail: greinecc@che1.che.umn.edu

Copyright 2001 John Wiley & Sons, Ltd.

concentration of hydrocolloid. The dilute beverage emulsion can almost be described as the concentrate being
dispersed in a second water phase, that is, from a
gum-solution water phase to a sugar-solution water
phase.3
Mechanisms of instability of beverage emulsions
include creaming, coalescence, flocculation and Ostwald
ripening. In the industry, the common term for creaming in bottled soft drinks is ringing because the flavour
emulsion separates from the soda, floats to the top and
shows a white creamy ring or oily ring at the neck of
the bottle. Coalescence implies localized disruption of
neighbouring droplets in aggregates, so that oil droplets
merge together to form large ones. This obviously leads
to a decreased number of droplets, enhances creaming
and eventually causes emulsion breakdown. Flocculation occurs when oil droplets of the dispersed phase
form aggregates or clusters without coalescence. These
aggregates behave as single large drops, and the rate
of creaming is accelerated. In emulsion concentrates, a
perceptible increase in viscosity can be observed when
flocculation occurs. In a soft drink system, droplet concentration is so low that flocculation is often reversible.
The aggregates can be readily redispersed when the interactions between droplets are weak.2 Ostwald ripening is
defined as the growth of larger droplets at the expense of
smaller ones, due to mass transport of soluble dispersed
phase through the dispersing medium. Ostwald ripening
is negligible unless the dispersed phase is at least sparingly soluble in the continuous phase. Since essential
oils are somewhat soluble in water, beverage emulsions
are prone to Ostwald ripening.4

8 R. A. BUFFO AND G. A. REINECCIUS

Particle size determination, centrifugation and elevated temperature storage were evaluated as potential
predictors of stability in dilute beverage emulsions. Stability was monitored by absorbance (loss of turbidity) at
400 nm. Storing emulsions at high temperatures gave the
most accurate prediction of emulsion stability. Storage
at 45 C increased the rate of loss of turbidity by factors
of 2.54 over room temperature storage. The accelerating effect was similar for emulsions with and without a
weighing agent in the dispersed phase, except that the
rate of loss of turbidity was 35 times greater for the
former.5
The objectives of this study were to assess the significance of the different mechanisms of instability in dilute
beverage emulsions as a function of temperature, and to
evaluate shelf-life and related kinetic parameters.

Materials and Methods

Materials

A commercial spray-dried gum acacia, RD 436 (Acacia

senegal ), was provided by Collodes Naturels International (Bridgewater, NJ). Cold-pressed orange oil Valencia (Florida) was supplied by Robertet Flavors (Piscataway, NJ). Sodium benzoate was purchased from Fisher
Scientific (Pittsburgh, PA), citric acid food grade from
Robertet Flavors (Piscataway, NJ) and sugar from United
Sugars Corporation (Minneapolis, MN). Deionized water
was used to prepare solutions and emulsions.

Emulsion Preparation

Concentrated emulsions were prepared according to the

following standardized formula:6 orange oil, 6.5%; gum
acacia, 20.0%; preservative (sodium benzoate), 0.1%;
deionized water, 73.4%.
No weighing agent was used in the oil phase. A solution of 25% (w/w) gum acacia was prepared from the
spray-dried commercial powder by hydrating it overnight
and gently mixing until complete dissolution. The moisture content of RD 436 was taken into consideration
for gum solution preparation. AACC air-oven method
44-19 was used to determine moisture content.7 Triplicate measurements gave a value of 8.56% moisture (db).
A coarsely emulsified premix was prepared by adding
the solubilized gum and other components (the additional water to lower gum concentration to 20%, w/w,
was used to dissolve the sodium benzoate) and homogenizing with a bench-top high-speed mixer (GriffordWood Mixer, Greerco Corporation, Hudson, NH), connected to a rheostat at 50% of full power for 5 min.
At this point, the pH of the premix was adjusted to
3.5 with 2 M citric acid. Fine emulsification (an average
Copyright 2001 John Wiley & Sons, Ltd.

droplet size <1 m and narrow particle size distribution) was achieved by running the premixes through a
high-pressure valve homogenizer (Microfluidizer Model
M-110Y, Microfluidics International Corporation, Newton, MA) at 89.6 MPa (13 000 psi) in a single pass. The
resulting concentrates were diluted to 0.25% (w/w) and
5% (w/w) in 10% sugar solution for emulsion stability
and particle size monitoring, respectively, and the pH
adjusted to 2.5 (pH meter GamRad, Novi, MI) with 2 M
citric acid. For the evaluation of kinetic parameters, samples of both dilute emulsions were stored at six different
temperatures: 4, 9, 23, 30, 37 and 55 C.
Measurements
Emulsion Stability

Dilute emulsions (0.25%, w/w; approximately 1 l) were

stored in 2 l plastic bottles and their stability monitored
by absorbance as measured by means of a Beckman DU
530 spectrophotometer at 500 nm (Beckman Instruments, Schaumburg, IL). Readings were taken until disappearance of 90% of initial absorbance, or until a week
from first reading (time D 0), whichever happened first.
A 10% sugar solution was used as a blank for absorbance
measurements. Frequency of readings was once a day for
samples stored at 4, 9 and 23 C, and twice a day for samples stored at 30, 37 and 55 C. Absorbance vs. time data
for each sample was fitted to a first-order model using the
Water Analyzer SeriesReaction Kinetics Program.8
A first-order model is characterized by the following
equation:
ln A D ln A0 k1 t
where t D time, A D absorbance at time D t, A0 D absorbance at time D 0 and k1 D the first-order rate constant.9 Emulsion stability end-point or time to breakage was computed from the above fitting equation at
A D 0.1 A0 . In order to differentiate statistically between
zero and first order, it is imperative to go beyond
50% of disappearance of the monitoring parameter.9
This was, in fact, the fundamental criterion to evaluate emulsion shelf-life. Thus, for those samples stored
at lower temperatures (expected to have a higher stability), absorbance readings were taken for as much time
as needed to reach such a statistical condition. The procedure described was considered more objective and
reliable than the ringing test given in the literature.1
Absorbance values were the average of two consecutive
readings. Single determinations of emulsion shelf-life
were conducted at each temperature.
Particle Size

Dilute emulsions (5%, w/w; approximately 250 ml) were

stored in 400 ml glass jars at the temperatures aforementioned and their mean particle size determined by

Flavour Fragr. J. 2001; 16: 712

SHELF-LIFE AND DESTABILIZATION IN DILUTE BEVERAGE EMULSIONS

static light scattering using a Malvern Series 2600 Particle Size Analyzer (Malvern Instruments Ltd., Malvern,
Worcestershine, UK). A single daily particle size determination was done per sample up to the end of shelf-life,
as described in the above section. The 5% (w/w) concentration was necessary to create enough obscuration
in the instrument throughout the prospective shelf-life
of samples at each temperature. Before readings, samples were vigorously hand-shaken and inverted in order
to distribute oil droplets eventually stratified by creaming, and to break eventual weak flocs (see later section
on mechanisms of destabilization). Aliquots were then
placed in a metal jar that circulated the sample through
the measuring glass cuvette of the instrument. A laser
beam was directed through the sample, scattered by the
droplets in a characteristic pattern dependent of their
size, and detected by an array of photodiodes located
behind the cuvette. A computer program calculated the
particle size distribution as the best fit between the measured scattered pattern and that predicted by light scattering theory.

interrelate temperature and emulsion stability. The wellknown Arrhenius relation is:
k D kA e

EA
RT

where kA D the Arrhenius equation constant, EA D the

activation energy, T D absolute temperature and R D the
universal gas constant. In practice, In (k) was plotted against the reciprocal absolute temperature, 1/T, to
obtain a straight line with a slope of EA /R.
Data on emulsion breakage at different temperatures
was used to construct a shelf-life plot according to the
following equation:
 D 0 e

bT

where  D shelf-life at absolute temperature T, the constant 0 D shelf-life at the y intercept, and b D the
slope of the shelf-life plot. In practice, for a relatively
small temperature range, a linear plot results for the relation log () vs. T: b becomes a constant and 0 the
shelf-life at 0 C.9 The Water Analyzer SeriesReaction
Kinetics Program8 was used to perform all computations.

Viscosity
Evaluation of Mechanisms of Destabilization

The viscosity of the 10% sugar solution at each storage

temperature was measured by rotational viscosimetry
(Rotovisco, Haake Inc., Saddle Brook, NJ). Samples
were placed in a thermostated measurement cell in the
narrow gap between two concentric cylinders. The inner
cylinder was driven at a constant torque or stress and
the resultant strain was measured as the speed at which
the inner cylinder rotated. This speed is governed by
the viscosity of the fluid between the plates, so that
the faster it spins at a given torque, the lower the
viscosity of the liquid being analysed. Viscosity was
computed from the shear stress/strain record according
to the dimensional parameters of the inner cylinder.
The NV sensor, classified as a co-axial cylinder system
with two gaps, was used to measure these very low
viscosity values. Single measurements were run per
sample.
Density

Densities of orange oil and 10% sugar solution were

measured at room temperature using hydrometers of
appropriate range (CMS Hydrometers, Curtis Matheson
Scientific, New York).

Evaluation of Kinetic Parameters

Based on the first-order reaction constants for emulsion breakage obtained at six different temperatures, as
described above, the Arrhenius approach was utilized to
Copyright 2001 John Wiley & Sons, Ltd.

Monitoring creaming throughout the temperature range

for each mean particle size vs. time data set was performed by means of Stokes law:
Stokes D

2gr 2 .2 1 /
91

where Stokes D mean droplet velocity (upwards), r D

mean particle size,  D density of the dispersed phase
(orange oil), 0 D density of the dispersing phase (10%
sugar solution), g D acceleration of gravity and 1 D
viscosity of the dispersing phase. No further correction
of velocity was attempted, e.g. with respect to emulsion
volume fraction or polydispersity.10
Coalescence and Ostwald ripening are both monitored
by following changes in mean droplet size and droplet
size distribution with time.10 A distinction between them
can be achieved through the following equations:
Coalescence:11
 
D1
1
ln
D tC
D0
3
where D0 and Dt D mean droplet sizes at time D 0
and time D t, respectively, and C D the rate of droplet
coalescence.
Ostwald ripening:4
r 3 D kt
where r D mean particle radius (taken as half the measured mean droplet size), t D time and k D the rate of
Ostwald ripening.

Flavour Fragr. J. 2001; 16: 712

10 R. A. BUFFO AND G. A. REINECCIUS

Table 1. Breakage time and first-order equation parameters for emulsion

destabilization within the temperature range 455 C
Temperature
. C/

r2

4
9
23
30
37
55

0.9353
0.9204
0.9288
0.9667
0.9690
0.8926

Standard
deviation

k
7.716E
8.688E
1.003E
1.856E
2.339E
6.448E

3
3
2
2
3
2

1.818E
2.555E
2.488E
2.812E
3.742E
3.106E

3
3
3
3
3
2

Breakage
time (h)
298.4
265.0
229.6
124.1
98.4
35.7

r 2 , Regression coefficient; k, first order rate constant.

The statistical package MacAnova12 was used to fit

these equations to the mean particle size vs. time data at
each storage temperature. Regression coefficients were
the statistical parameters employed to evaluate the significance of the two mechanisms of destabilization so
that the greater the coefficient, the more significant the fit
of the corresponding equation to the experimental data.
As indicated in the Introduction section, droplet concentration in dilute beverage emulsions is low enough for
flocculation to be considered a reversible phenomenon.
Intense agitation of 5% (w/w) emulsions before measurement of particle size was assumed sufficient to break
eventual weak flocs, and flocculation was consequently
discarded as a significant mechanism of destabilization.

Results and Discussion

Figure 1. Fit of the Arrhenius equation to emulsion

destabilization data. Slope D 3.703E C 3 1.587E C 3.
Intercept D 8.290 5.325. r 2 D 0.9132. Std error D
0.2648. Activation energy D 7.359 3.153 kcal/mol

Kinetics and Shelf-life

Characterization parameters of the first-order fitting

equations to absorbance vs. time data and the corresponding breakage times throughout the temperature
range studied are given in Table 1. Closeness of breakage time vs. temperature data to the fitting line in the
Arrhenius plot (Figure 1) was a significant hint that similar mechanisms of emulsion destabilization occurred
throughout the temperature range studied. The equation
for the line was:
ln kA D 8.29

3.70 103

1
T

[r 2 D 0.9132]

with EA D 7.357 kcal/mol.

The shelf-life plot of dilute emulsion breakage
(Figure 2) responded to the following parameters:
b D 0.0415

0 D 3.486 107

 D 3.486 107 e

0.0415T

[r 2 D 0.9374]

Mechanisms of Destabilization

Creaming rates as a function of temperature and time

are presented in Table 2. Expectedly, upward velocity
Copyright 2001 John Wiley & Sons, Ltd.

(as indicated by the negative sign) increased with time

because of growth of the particles, and temperature
because of the decrease in viscosity. Density of oil and
water phases were considered constant throughout the
temperature range because of their very small variation
with temperature. Viscosity of the 10% sugar solution in
which 5% of emulsion concentrate was dispersed varied
from 1.21 cp at 4 C to 0.72 cp at 55 C. As an example,
consider the creaming velocities at time D 24 h from
preparation of dilute emulsions: creaming at 55 C was
10 times greater than at 4 C.
Evaluation of Ostwald ripening and coalescence throughout the temperature range is shown in Table 3. The
significance of Ostwald ripening as a key mechanism of
destabilization in dilute beverage emulsions was clearly
evident by the high regression coefficients obtained
in the fit of its characterizing equation to the experimental data. This confirms the results from previous researchers13 who found Ostwald ripening as the
main destabilization mechanism in limonene-in-water
emulsions. Some typical methods cited in the literature to control Ostwald ripening include narrowing the
droplet size distribution (to avoid gradients of solubility of the dispersed phase into the bulk phase since
solubility increases with decreasing radius), lowering

Flavour Fragr. J. 2001; 16: 712

SHELF-LIFE AND DESTABILIZATION IN DILUTE BEVERAGE EMULSIONS

11

amount of emulsifier in the system. Decreasing Ostwald ripening by increasing the gum acacia layer on
the particles is problematic, since the emulsion is ultimately diluted so greatly. In fact, dilution leads to a
shrinkage of this layer.14 Thus, narrowing the droplet
distribution appears to be the most effective method
of minimizing Ostwald ripening in dilute beverage
emulsions.
Regression analysis also indicated some significance
for coalescence. Gum acacia has been reported to be
quite effective in preventing destabilization by coalescence.3 The formation of a thick adsorbed layer around
the oil droplets keeps them apart far enough by steric
interaction, which also minimizes attractive Van der
Waals forces. In this study, the increase in creaming
rates because of the lack of a weighing agent in the oil
phase may have caused higher rates of coalescence as a
result of more numerous thermodynamically favourable
collisions among droplets. This observation was supported by the experimental data because particle growth
was greater and faster at higher temperatures. In addition, progressive accumulation of droplets at the top of
the sample due to creaming may have also caused coalescence as a consequence of prolonged contact, especially
in those samples stored at higher temperatures (higher
rates of creaming).
Finally, regression coefficients for both Ostwald ripening and coalescence were comparable throughout the
temperature range, a clear indication of the occurrence of
similar mechanisms of destabilization. This is in fact the
strongest argument to justify running accelerated tests
of stability at higher temperatures and provides a solid
physicochemical explanation to data previously reported
in the literature.5

Figure 2. Shelf-life plot of dilute beverage emulsion

breakage

the interfacial tension (in direct relationship with Ostwald ripening rate) or increasing layer thickness (to
retard diffusion of the dispersed phase through the
layer of emulsifier around the droplet).4,10 The last
two methods are evidently linked to the kind and

Table 2. Evolution of creaming velocity (mm/h) as a function of time and temperature

in dilute beverage emulsions
Time (h)
0
24
48
72
96
168
192

4 C

9 C

0.0018
0.0084
0.0127
0.0142
0.0174
0.0232
0.0268

23 C

0.0019
0.0112
0.0151
0.0190
0.0207
0.0330
0.0469

0.0023
0.0174
0.0243
0.0309
0.0350
0.0602

30 C
0.0024
0.0205
0.0333
0.0404
0.0468

37 C

55 C

0.0026
0.0443
0.0500
0.0657

0.0031
0.0807
0.0921

Table 3. Regression coefficients for Ostwald ripening and coalescence characterizing equations in dilute beverage emulsions within
the temperature range 455 C
Temperature . C/

r 2 (Ostwald ripening)

r 2 (Coalescence)

4
9
23
30
37
55

0.981
0.911
0.964
0.986
0.924
0.877

0.671
0.731
0.646
0.681
0.588
0.675

Copyright 2001 John Wiley & Sons, Ltd.

Flavour Fragr. J. 2001; 16: 712

12 R. A. BUFFO AND G. A. REINECCIUS

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Copyright 2001 John Wiley & Sons, Ltd.

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