A Comparison of the Stability of Beverage

Cloud Emulsions Formulated with Different

Gum Acacia- and Starch-Based Emulsifiers
S.J. Reiner, G.A. Reineccius, and T.L. Peppard

Abstract: The performance of several hydrocolloids (3 gum acacias, 1 modified gum acacia, and 3 modified starches) in
stabilizing beverage emulsions and corresponding model beverages was investigated employing different core materials,
emulsifier usage levels, and storage temperatures. Concentrated emulsions were prepared using orange terpenes or
Miglyol R
812 (comprising medium-chain triglycerides, MCT) weighted 1:1 with ester gum, stored at 25 or 35 ◦ C, and
E: Food Engineering &

analyzed on days 0, 1, and 3. On day 3, model beverages were made from each emulsion, stored at both temperatures, and
Physical Properties

analyzed weekly for 4 wk. Stability of concentrated emulsions was assessed by measuring mean particle size and by visual
observations of ringing; beverage stability was judged similarly and also by loss of turbidity. Particle size measurements
showed concentrated emulsions containing gum acacia or modified gum acacia with either core material were stable over
3 d storage at both temperatures whereas those made with modified starches were not, destabilization being faster at 35 ◦ C.
Beverages based on orange terpenes, in contrast to Miglyol, yielded smaller mean particle sizes, both on manufacture and
during storage, regardless of hydrocolloid used. Visual observations of ringing generally supported this finding. Modified
gum acacia was evaluated at both recommended and higher usage levels, stability increasing in the latter case. In general,
all gum acacia and modified gum acacia emulsifiers were superior in stability to those based on modified starches, at
either temperature, for orange terpene-based beverages. In Miglyol-based beverages, similar results were seen, except 1
modified starch performed as well as the gum acacia products.
Keywords: beverage cloud emulsion, gum acacia, modified gum acacia, modified starch, physical stability

Introduction
Beverage emulsions are oil-in-water (O/W) emulsions, which
can generally be categorized as either cloud emulsions (imparting
opacity) or flavor emulsions (providing flavor in addition to cloudi-
ness) (Tan 1997; McClements 1999; Reineccius 2006). Emulsions
are unstable by nature and this represents an ongoing challenge
for beverage manufacturers. Beverage emulsions are unique to the
food industry, because they are typically sold to beverage man-
ufacturers as emulsion concentrates, whereas they are consumed
by the public in a highly diluted state. It is, therefore, essential
that beverage emulsions remain stable in both forms, for at least
6 mo according to beverage industry standards. Strategies to in-
crease the stability of beverage emulsions generally comprise the
use of homogenization, weighting agents (to raise the density of
the oil phase), and emulsifiers (with or without additional surfac-
tants).
A finished beverage typically consists of a small percentage of
beverage emulsion dispersed in water, along with a number of
other ingredients, including caloric and/or high-intensity sweet-
ener, acidulant (to add taste and lower pH), dye (for color), and
preservative (to prevent microbial spoilage). Although the emul-
MS 20090724 Submitted 7/28/2009, Accepted 3/2/2010. Authors Reiner and
Reineccius are with Dept. of Food Science & Nutrition, Univ. of Minnesota, 1334
Eckles Ave., St. Paul, MN 55108, U.S.A. Author Peppard is with Robertet Flavors,
Inc., 10 Colonial Dr., Piscataway, NJ 08854, U.S.A. Direct inquiries to author
Reineccius (E-mail: greinecc@umn.edu).
sion has been diluted, the beverage as a whole is still inherently un-
stable and, given unfavorable circumstances, can clear (or “ring”)
by means of destabilizing mechanisms such as creaming, floccu-
lation, coalescence, or so-called Ostwald ripening, in all cases
tending to form an unsightly product.
Gum Arabic (gum acacia) is a hydrocolloid that traditionally
has been the material of choice for emulsifying and stabilizing
beverage emulsions. While gum acacia comprises mostly arabino-
galactan (AG; approximately 90%), its functionality as an excellent
emulsifier is generally ascribed to a small but significant protein
content (1% to 3%) originating mainly from its arabinogalactan
protein fraction (AGP; approximately 10%) and to a lesser extent
from its glycoprotein fraction (GP; approximately 1%) (Randall
and others 1988; Mahendran and others 2008). Recent research
has also implicated a low but apparently significant level of lipids
in helping to explain gum acacia’s reputation as an outstanding
emulsifier (Yadav and others 2007a). There are 2 botanical species
approved for commercial use as sources of gum acacia: Acacia sene-
gal and Acacia seyal. Gum acacia derived from these species differ
in emulsifying capability, with that from A. senegal generally being
considered the industry “gold standard” for stabilizing beverage
emulsions (Randall and others 1988).
There are many issues related to the commercial use of gum
acacia as a stabilizer in beverage emulsions, including quality, avail-
ability, and cost. As the exported volume of A. senegal from one of
its principal sources, Sudan, has decreased in recent years (World
Bank 2007), the demand worldwide has increased due to tremen-
dous growth in beverage sales, especially in the United States
(Gitlitz and Franklin 2007). Therefore, the price of A. senegal gum

C 2010 Institute of Food Technologists

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E236 Journal of Food Science r Vol. 75, Nr. 5, 2010 doi: 10.1111/j.1750-3841.2010.01625.x
Further reproduction without permission is prohibited
Stability of beverage cloud emulsions . . .
has risen dramatically (Purcell 2005). There is also much variability
in the emulsifying capability derived from different batches of A.
senegal because it is harvested from a natural source. To alleviate
these problems, manufacturers are evaluating various alternative
materials in the hope of finding more reliable, cost-effective, and
consistent emulsifiers that could lead to less dependence on gum
acacia. Products that have recently been studied as potential re-
placements for A. senegal include modified starch, modified A.
seyal, fenugreek, corn fiber gum, potato protein, β-lactoglobulin,
soy and whey protein isolates, sodium caseinate, and sugar beet
pectin (Kim and others 1996; Huang and others 2001; Tesch
and others 2002; Ward 2002; Harnsilawat and others 2006; van
Koningsveld and others 2006; Yadav and others 2007b; Nakauma
and others 2008; Siew and Williams 2008). However, most of
these products have yet to be commercialized.
The flavor industry generally uses either orange terpenes or
medium-chain triglyceride (MCT) as a particulate phase in mak-
ing cloud emulsions and previous research has demonstrated that
the type of oil phase can have a very significant effect on how
an emulsifier interacts with it affecting both the initial particle
size and the subsequent stability (Dickinson and others 1991;
Chanamai and others 2002). Thus, we were interested in studying
the efficacy of several commercially available emulsifiers with both
oil types. For background, Dickinson and others (1991) conducted
studies evaluating the influence of oil type (hexadecane, limonene,
or orange oil) and type of gum acacia on the initial and over time
droplet size distributions of emulsions. A primary conclusion of
this work was that both oil type and emulsifier selection (different
gum acacias in this case) influenced the initial particle size distri-
bution and stability during storage. For example, a particular gum
acacia gave excellent stability to the hexadecane-based emulsion
but performed very poorly with emulsions based on limonene
or orange oil. A controlling factor in emulsifier performance was
how quickly and how efficiently a given gum acacia interacted
with the oil phase to lower interfacial tension. The primary mode
of instability was determined to be coalescence.
Chanamai and others (2002) also evaluated the importance of
oil type (hexadecane, decanol, decane, and decanol:hexadecane
blends) and emulsifier type (gum acacia compared with Tween
20) on particle growth in emulsions over time. They used these
oil phases to determine how the polarity and solubility of the oil
phase influence the mechanism (Oswald ripening and coalescence)
and the extent of particle size instability. They found that emul-
sions made with a very nonpolar and water insoluble oil phase
(hexadecane) were quite stable over time irrespective of the type
of emulsifier used. Emulsions based on an oil phase also having
low polarity but relatively greater water solubility (decane) were
stable to coalescence but not Oswald Ripening again irrespective
of the emulsifier used. Finally, the stability of emulsions made with
an oil phase with relatively high solubility and polarity (decanol)
was dependent upon the emulsifier used. For example, emulsions
based on decanol and stabilized with Tween 20 were stable in the
concentrated form but not on dilution. Decanol-based emulsions
made with gum acacia were very unstable with both Ostwald
Ripening and coalescence occurring. The authors postulated that
the more polar oil phase (decanol) did not interact well with gum
acacia thereby permitting coalescence to occur.
The aim of the work described in this article was to evalu-
ate the performance of beverage emulsions formulated using a
number of commercially available potential replacements for A.
Senegal and the 2 most commonly used oil phases (MCT and
orange terpenes). The emulsifiers tested, namely, several modi-
fied starches and a modified A. seyal, are highly consistent, readily
available, and cost-effective, all of which make them very attrac-
tive to beverage emulsion manufacturers and users alike. In this
work, modified starch was starch esterified with octenyl succinic
anhydride (OSA) (Tesch and others 2002) while modified gum
acacia (TicamulsionR ) is a relatively new OSA-modified A. seyal
(Ward 2002). In both cases, treatment with OSA potentially im-
proves emulsifying capability by increasing overall hydrophobicity
(Randall and others 1988; Ward 2002).
Materials and Methods
Materials
TIC Gums, Inc. (Belcamp, Md., U.S.A.) donated samples of pre-
hydrated gum acacia spray dry FCC powder (A. senegal), Bev-101
GR, and TicamulsionR A-2010. PurityR Gum 2000 and PurityR
E: Food Engineering &
Physical Properties
Gum 1773 (Natl. Starch Corp., Bridgewater, N.J., U.S.A.), Mira
MistR 662 (Tate & Lyle, Decatur, Ill., U.S.A.), and EficaciaTM
(Colloides Naturels Intl., Bridgewater, N.J., U.S.A.) were also
received as gifts. The various emulsifiers used in this study are
described in Table 1. Orange oil terpenes were obtained from
Citrus and Allied Essences Ltd. (Lake Success, N.Y., U.S.A.) and
MiglyolR 812, an MCT, was purchased from Sasol (Houston, Tex.,
U.S.A.); ester gum was obtained from J.H. Calo Co. (Westbury,
N.Y., U.S.A.). Miglyol 812 is a combination of triglycerides based
on the following fatty acid composition: C6:0 max. 2%; C8:0 50% to
65%; C10:0 30% to 45%; C12:0 max. 2% and C14:0 max. 1% (Sasol,
Houston, Tex., U.S.A., tech sheet). The orange terpenes used
were comprised primarily of limonene (95.6%); myrcene (2.8%);
sabinene (2.8%); α-Pinene (0.9%); and octanal (0.2%) as measured
by gas chromatography. Sodium benzoate and citric acid (Sigma
Aldrich, St. Louis, Mo., U.S.A.), granulated sugar (Cub Foods,
Minneapolis, Minn., U.S.A.), and granulated FD&C Yellow #6
(Sensient Colors, Milwaukee, Wis., U.S.A.) were purchased and
used for making beverages from the concentrated emulsions. All
solutions and emulsions were prepared using distilled water.
Prediction of solubility and polarity
Solubility and polarity values for selected components of
Miglyol and orange terpenes were calculated using Molecular
Designer V:5.1.9 (NorGwyn Montgomery Software, Inc., North
Wales, Pa., U.S.A.).
Beverage emulsion preparation
Concentrated beverage emulsions were prepared in accordance
with manufacturer’s specifications, using emulsifiers at both rec-
ommended and, in some cases, also higher levels (see Table 1).
Separate sets of emulsions were prepared using orange terpenes
and Miglyol, respectively, as core materials. All emulsions were
Table 1–Emulsifiers used in study.a
Emulsifier (trade name) Description Usage level(s)
FCC powder Pure Acacia senegal 16%
Eficacia Pure gum acaciab 7%; 16%
Bev-101 GR Gum acacia blendb 16%
Ticamulsion A-2010 Modified gum acacia 7%; 16%
Purity Gum 2000 Modified starch 12%
Purity Gum 1773 Modified starch 12%
Mira Mist 662 Modified starch 12%
a
Emulsion concentrates comprised the noted % of emulsifier, 10% weighted oil (orange
terpenes or Miglyol, weighted 1:1 with ester gum), 5% FD&C Yellow #6, and distilled
water q.s. to 100%.
b
Proprietary composition.
Vol. 75, Nr. 5, 2010 r Journal of Food Science E237
 Stability of beverage cloud emulsions . . .
made in duplicate for each oil. All starches and gum acacias were
thoroughly mixed with distilled water using an overhead mixer
prior to homogenization. Granulated Yellow #6 was added by
weight to the starch/gum solutions and was thoroughly mixed.
A 1:1 ratio of oil to ester gum was used to prepare the weighted
oil before emulsification into starch or gum solutions. The pre-
emulsions were prepared by slowly adding the weighted oil to the
starch or gum solution using a high-shear mixer (Greerco Corp.,
Hudson, N.H., U.S.A.) at 6000 to 7000 rpm for 2 min. The oil
and starch/gum solutions were at room temperature when mixed.
All samples were then homogenized by passing them once each
through a MicrofluidizerR (Model M-110Y, Microfluidics Corp.,
Newton, Mass., U.S.A.) at a pressure of 13000 psig.
Following homogenization, all emulsions were stored in test
tubes at both 22 and 35 ◦ C and analyzed on days 0, 1, and 3. The
E: Food Engineering &
effects of each emulsifier in the beverage emulsion concentrates
Physical Properties
were examined by following changes in mean droplet diameter
(MDD) and by visual observations of ringing.
Beverage preparation
Beverages were made from emulsion concentrates 3 d after
emulsion preparation according to the following formulation: su-
crose (10%), citric acid (0.3% or pH 3.6), sodium benzoate (0.1%),
beverage emulsion (0.5% or 2%), and distilled water (q.s. to 100%).
The concentrates were mixed before an aliquot was removed and
diluted into the beverage base. Seven 8 oz. plastic bottles were
prepared from each emulsion: 2 bottles were prepared with 0.5%
emulsion and were used for the ringing and turbidity tests, and
5 bottles were prepared with 2% emulsion in order to obtain
an obscuration sufficiently high to permit particle size analysis.
One bottle was used for each week of particle size analysis so as
not to disturb the emulsions during continued storage. Beverages
were kept in both 22 and 35 ◦ C storage and analyzed weekly for
4 wk. They were evaluated for changes in MDD, loss in turbidity,
and changes in overall appearance, for example, the presence of
ringing.
Beverage emulsion stability
Particle size analysis. MDD was determined using a Mas-
tersizer S (Malvern Instruments, Southborough, Mass., U.S.A.)
at an obscuration of between 20% and 25%. Measurements
were recorded using the value (termed MDD throughout
manuscript) corresponding to the D[4,3] volume/mass moment
mean (Malvern Instruments 2009) also known as the De Brouckere
mean diameter. The lower limit of size identification for this in-
strument is 0.50 μm and the upper size limit is 900 μm.
Emulsion concentrates. All emulsion samples were analyzed in
duplicate. The MDD of each emulsion concentrate was measured
on days 0, 1, and 3 (at both 22 and 35 ◦ C). The emulsions were
mixed before sampling. To determine the MDD, emulsion was
added dropwise to the sample collector until the required obscu-
ration was reached.
Beverages. To measure the MDD of beverages, samples were
gently mixed (by turning bottles upside-down twice) and then
poured into the sample collector until an obscuration of 20% to
25% was reached. All samples were analyzed in duplicate.
Statistical analysis of particle size data was performed on both
emulsion concentrates and beverages. Data collected from the end
of each storage period (day 3 and week 4, respectively) were the
only data chosen for statistical analysis. The results were subjected
to a one-way analysis of variance (ANOVA). Where there were
significant differences, individual treatments were compared using
E238 Journal of Food Science r Vol. 75, Nr. 5, 2010
Fisher’s least significant difference (LSD) test. All statistical analysis
was performed using Statgraphics Centurion XV statistical soft-
ware (Herndon, Va., U.S.A.) at a significance level of α = 0.05.
Changes in turbidity of beverages. Change in turbidity
over time was measured using a spectrophotometer (Spectronic
20, formerly Bausch & Lomb, now Milton Roy, Spectronic In-
struments, Inc., Rochester, N.Y., U.S.A.) at a wavelength of
400 nm. Since the added dye increased the absorbance tremen-
dously, all samples had to be diluted in order to be able to read the
absorbance. To prepare the dilution, 1 mL of beverage was care-
fully pipetted from the bottom of each bottle so as not to disturb
the sample, and then diluted 1:10 with distilled water. Distilled
water served as the blank. Although this method was chosen for
its simplicity, slight variation in sampling technique can often lead
to poor reproducibility.
Visual observations of ringing. Visual appearance was as-
sessed by means of the so-called “ringing” test. A white ring
appears at the neck of the bottle when sufficient creaming has
occurred in a beverage. Any beverage that formed a ring on stor-
age was considered unstable. Both the beverage concentrates and
the resulting beverages were checked for signs of ringing during
storage, respectively, daily for 3 d and once per week over 4 wk.
Rings that formed were easily identified since they were white in
contrast to the dyed solution. Digital photographs were also taken
at each time interval to document any changes. In an attempt
to visualize rings more easily, beverages were also stored in glass
Babcock bottles; unfortunately, this did not help.
Results and Discussion
In searching for a reliable, economic, and high-quality alterna-
tive to A. senegal for use in stabilizing beverage cloud emulsions, a
number of hydrocolloids were evaluated, including 3 gum acacias,
3 modified starches, and 1 modified gum acacia. The performance
of these hydrocolloids in emulsion concentrates, as well as when
diluted in corresponding model beverages, was investigated using
2 different core materials (orange oil terpenes and Miglyol 812),
different emulsifier usage levels (recommended and higher), and
2 storage temperatures (25 and 35 ◦ C). Stability of beverages and
beverage emulsions was studied over, respectively, 4 wk and 3 d, by
monitoring changes in MDD using laser light diffraction, loss of
turbidity by spectrophotometry, and formation of any undesirable
ringing based on visual observation.
Particle size analysis
Orange terpene-based concentrated emulsions. The
MDD of the orange terpene emulsion concentrates on day 0
ranged from 0.65 μm to 0.95 μm for the gum acacia products and
from 0.72 μm to 1.64 μm for the modified starches (Figure 1).
The gum acacia-based emulsions were unimodal in shape, gener-
ally exhibiting a relatively tight particle size distribution (Figure 2,
top). Of the gum acacias, the Ticamulsion product gave a slightly
wider particle size distribution than the other gums. All of the
modified starches yielded emulsions with a much broader parti-
cle size distribution and a nearly flat top to the peak distribution
(Figure 2, middle): they looked as if they were pseudo bimodal
distributions (more will be said about the particle size distributions
later in the manuscript).
The gum acacia-based emulsions showed no increase in MDD
over 3 d at either storage temperature, whereas those based on
starches exhibited increases at both temperatures, indicating parti-
cle instability (Figure 1).
Stability of beverage cloud emulsions . . .

A. senegal Figure 1–MDD of orange terpene-based

2.2 emulsion concentrates over 3 d of storage at
Efic 16%
Efic 7% 22 ◦ C. Series with different letters denote
2.0 Tica 16% significant differences between samples at day
3 (P < 0.05). Note: a = A. senegal, Eficacia 7%,
Mean Droplet Diameter, MDD (um)

Tica 7%
PG2000
Eficacia 16%, Ticamulsion 7%, and Ticamulsion
1.8 16%.
e Bev101
PG1773
1.6
Mira Mist

1.4

1.2 d

1.0
c

E: Food Engineering &

b

Physical Properties
0.8

}a
0.6
0 1 2 3 4
Days of Storage

During the 3 d of storage, it appeared that modified gum acacia

Figure 2–Typical particle size distributions of freshly prepared terpene-
based emulsion concentrates (top: A. senegal; middle: Purity Gum 2000) a dilute solution compared to the situation in the emulsion con-
and an aged emulsion (bottom: Purity Gum 2000 at 3 d).
was comparable in stability to gum acacia products based on A.
senegal. It was also observed that Purity Gum 2000 (PG 2000) had
an MDD of <1 μm, which is generally considered small enough
to permit stable beverage emulsions (Reineccius 2006), although
it was significantly larger than the gum acacia products by day
3 (P < 0.05). Modified gum acacia at either usage level showed
no statistical differences from the other 3 gum acacia products
after 3 d of storage at either temperature (P > 0.05). The MDD
of the emulsion concentrates based on modified starches tended
to increase slightly during storage (Figure 1) although the particle
size distribution remained similar (Figure 2, middle compared with
bottom).
Storage temperature apparently did not affect the gum acacia-
based emulsions, as they showed no change in MDD at either
temperature (data not shown). In contrast, the modified starch
emulsions increased their MDD at a slightly faster rate in 35 ◦ C
storage compared with storage at 22 ◦ C (Figure 3).
Orange terpene-based beverages. The initial MDD of the
orange terpene emulsion-based beverages ranged from 0.65 μm
to 0.96 μm for the gum acacias and from 0.92 μm to 1.88 μm
for the modified starches (Figure 4). Similar as was observed for
the emulsion concentrates, the MDD and particle size distribu-
tion of the gum acacia products did not change during the (4 wk)
storage period, at either temperature, albeit the Bev101 product
did show a very slight decrease. However, the MDD of the mod-
ified starch systems decreased to a greater or lesser extent over
4 wk (again retaining approximately the same particle size dis-
tribution as was observed in the freshly made concentrate—data
not shown). For example, Purity Gum 1773 (PG 1773) had an
initial MDD of 1.28 μm, whereas after 4 wk it had an MDD of
1.06 μm. Similar effects were seen in 35 ◦ C storage (data not
shown). Since this phenomenon was observed across duplicate
samples and at both temperatures, there are numerous data points
supporting this result. We propose that this may be due to loss of
hydrocolloid from the surface of particle droplets once placed in
centrate. Alternatively, this apparent anomaly could arise from an

Vol. 75, Nr. 5, 2010 r Journal of Food Science E239

 Stability of beverage cloud emulsions . . .

instrumental issue. Since the particle size cutoff for this instrument
is 0.5 μm, particles with a diameter smaller than this will not be
observed initially. However, in the event of such under-sized par-
ticles growing to above 0.5 μm in dia during storage (at which
point they would be counted) this might be expected to skew the
MDD just enough to show an overall decrease in comparison to
the actual increase in MDD that likely occurred in the modified
starch-based emulsions.
Concerning the appropriate usage level of the 2 specialty gum
acacias, it was determined that Eficacia and Ticamulsion at 16%
had smaller MDDs throughout the 4 wk compared with results
seen at the 7% usage level, although all results were statistically
similar to each other (P > 0.05). The MDD of emulsions made
with the modified starch PG 2000 was statistically similar to both
usage levels of modified gum acacia Ticamulsion (7% and 16%)
E: Food Engineering &
ever, since the MDD remained at <1 μm throughout storage, PG
2000 does appear to exhibit characteristics of a stable emulsion.
Furthermore, several studies have already shown that PG 2000,
in particular, might be an acceptable substitute for A. senegal. For
example, Tesch and others (2002) were able to produce stable
emulsions of PG 2000 (5%, w/w) and vegetable oil with an MDD
of 1 μm. Dluzewska and others (2005) also produced emulsions
using PG 2000 (8%, w/w) and essential oil with an initial MDD of
<1 μm. These emulsions were not particularly stable though and
MDD increased to approximately 2 μm over 12 wk of storage. The
work of these 2 groups supports the findings of the present study,
although the methodology for producing the emulsions (that is,
usage level of starch and oil, homogenization pressure, use/type
of weighing agent, and so forth) varies greatly among studies, so
direct comparisons are not possible.

as well as to the gum acacia blend Bev101, but it was statistically To expand upon the influence of these emulsifiers on particle
Physical Properties

different from all of the unmodified gum acacia products. How- size distribution, a direct relationship between MDD and particle

2.2 Mira Mist 35°C Figure 3–Effect of temperature on the MDD of

Mira Mist 22°C starch-based emulsion concentrates (orange
PG1773 35°C
terpenes) over 3 d of storage.
2.0
PG1773 22°C
PG2000 35°C
Mean Droplet Diameter, MDD (um)

1.8 PG2000 22°C

1.6

1.4

1.2

1.0

0.8

0.6
0 1 2 3 4
Days of Storage

2.2 A. senegal Figure 4–MDD of beverages prepared with

Efic 16% orange terpene-based emulsions over 4 wk of
Efic 7% storage at 22 ◦ C. Series with different letters
2.0 Tica 16% denote significant differences between samples
Tica 7% at week 4 (P < 0.05). Note: a = A. senegal,
Eficacia 16% and Eficacia 7%, and ab =
Mean Droplet Diameter, MDD (um)

1.8 PG2000
Ticamulsion 16% and Ticamulsion 7%.
Bev101
e
PG1773
1.6
Mira Mist

1.4

1.2

d
1.0
c
0.8 bc
ab
a
0.6
0 1 2 3 4 5
Weeks of Storage

E240 Journal of Food Science r Vol. 75, Nr. 5, 2010

Stability of beverage cloud emulsions . . .

size distribution (expressed as standard deviation [SD] of the par-
ticle size distribution in this article) is well documented in the
literature (McClements 1999). Essentially, a wider distribution in-
dicates a more polydisperse emulsion that is likely to be less stable
than a narrowly distributed and monodisperse emulsion having
the same MDD. In the present study, both small MDD values and
narrow distributions were observed for A. senegal, Eficacia (7%
and 16%) and Ticamulsion (7% and 16%) in both the emulsion
concentrates and beverages. The initial SD of the distribution for
these emulsifiers was 0.13 or less. The emulsifiers that had slightly
larger MDD values also had wider particle size distributions. For
example, Bev101 had an average initial SD of 0.30, while Mira
Mist had a very wide distribution with initial average SDs of 1.38
for the emulsion concentrate and 1.47 for the beverage. PG 2000
had SDs of 0.13 for the concentrate and 0.31 for the beverage.
The orange terpenes contained components ranging in solubility
from 2.67 × 10−3 to 7.36 × 10−1 g/L and polarities ranging from
0.74 to 3.05. Thus, the Miglyol was much less soluble and gener-
ally more polar than the orange terpenes. Based on the literature
cited previously, one would expect the Miglyol-based emulsions
to be relatively stable to Oswald ripening but potentially more
susceptible to coalescence than the emulsion made based on or-
ange terpenes. The higher polarity of the Miglyol would result
in poorer interaction with the emulsifiers and thereby gives lesser
protection against coalescence relative to the orange terpene-based
emulsions (Chanamai and others 2002).
The MDDs of the concentrated emulsions made with Miglyol
were greater than the corresponding emulsions made with or-
ange terpenes. This would tend to make Miglyol-based emulsions
less stable than orange terpene-based emulsions. (In contrast, the

E: Food Engineering &

PG 1773 was “pseudo” bimodal in distribution. Of the modi- Miglyol-based emulsions would be greater in density than the

fied starches, PG 2000 yielded the smallest MDD and narrowest
particle size distribution.
Miglyol-based concentrated emulsions. Since the litera-
ture has shown that the type of oil phase may strongly influence
the efficacy of an emulsifier, we considered it necessary to evaluate
the performance of these emulsifiers with emulsions made with
both Miglyol and orange terpenes. In order to help explain the
data obtained, it is necessary to consider the solubility and polarity
of these 2 oil phases (see predicted values listed in Table 2). The
Miglyol we used was a blend of MCTs ranging in solubility from
4.90 × 10−13 to 6.45 × 10−6 g/L and polarities from 4.61 to 6.87:
a material which is extremely insoluble and yet is relatively polar.
Physical Properties
equivalent orange terpene-based emulsions, which might be ex-
pected to offer greater rather than lesser stability for the former.)
A possible reason for the larger MDD is the higher viscosity of
Miglyol. Its viscosity without ester gum is in the range of 27 to
33 mPa·s whereas orange terpenes have a viscosity of approx-
imately 1.3 mPa·s. With the addition of ester gum, both oils
increase in viscosity (Chanamai and McClements 2000) with
Miglyol becoming extremely viscous. The relationship between
viscosity and efficient droplet disruption during homogenization
is that droplets become increasingly more difficult to disrupt when
the viscosity ratio (dispersed viscosity [ηD]/continuous viscosity
[ηC]) is greater than 5 (Walstra 1996; Chanamai and McClements

Table 2–Predicted solubility and polarity values for selected components of Miglyol 812 and orange terpenes.
Miglyol 812a Orange terpenesa
b c
Triglyceride component Solubility (g/L) Polarity Orange oil component Solubilityb (g/L) Polarityc
1x C6 , 2x C8 6.4453 × 10−6 6.70848 Limonene 5.801 × 10−3 0.97561
3x C8 (Tricaprylin) 6.2537 × 10−7 6.86732 Myrcene 2.667 × 10−3 1.13665
3x C10 (Tricaprin) 5.5998 × 10−10 5.84957 α-Pinene 4.858 × 10−2 0.735612
3x C12 (Trilaurin) 4.8990 × 10−13 4.60551 Sabinene 1.545 × 10−2 0.798991
n-Octanal 7.364 × 10−1 3.04569
a
Proportions of components listed in Materials and Methods section.
b
Klopman and Zhu (2001).
c
Hansen (2007).

A. senegal Figure 5–MDD of Miglyol-based emulsion

2.2
f Efic 7% concentrates over 3 d of storage at 22 ◦ C.
Efic 16% Series with different letters denote significant
2.0 Tica 7% differences between samples at day 3 (P <
Tica 16%
0.05). Note: bc = Purity Gum 2000 and
Mean Droplet Diameter, MDD (um)

Ticamulsion 16%, and de = Eficacia 7% and

Bev101
1.8 Ticamulsion 7%.
PG1773
PG2000
1.6 Mira Mist

1.4 e

} de
1.2
cd
} bc
1.0 b

0.8 a

0.6
0 1 2 3 4
Days of Storage

Vol. 75, Nr. 5, 2010 r Journal of Food Science E241

 Stability of beverage cloud emulsions . . .
2000). A 2nd factor may be the rate at which the emulsifier comes
to the lipid:water interface thereby affording protection against
coalescence. Unfortunately, we did not gather any data on inter-
facial tension or rate of change of this factor across emulsifiers or
oil types so we cannot offer any insight into the role of this factor
in causing a larger MDD at the time of manufacture.
The initial MDD of the Miglyol-based emulsion concentrates
ranged from 0.99 μm to 1.33 μm for all emulsifiers except Mira
Mist (see Figure 5). Using Mira Mist as emulsifier resulted in par-
ticles with a much larger mean dia, 1.86 μm, which increased to
2.16 μm over the course of 3 d storage at 22 ◦ C. The particle size
distributions of these emulsions were very broad with significant
proportions of the distribution extending to a droplet dia of 10 um
(Figure 6). The broad dispersion of the distribution made it dif-
ficult to determine if Oswald ripening or coalescence was the
E: Food Engineering &
primary mode of instability. (However, as noted above, the very
Physical Properties
low solubility of Miglyol works against Ostwald ripening being
the cause of instability.) Using either Eficacia or A. senegal as
Figure 6–Initial particle size distributions of Miglyol-based emulsion con-
centrates (top: Ticamulsion 7%; middle: Ticamulsion 16%; bottom: Mira 4 wk storage period, all of the orange terpene-based beverages
Mist).
E242 Journal of Food Science r Vol. 75, Nr. 5, 2010
emulsifiers (in each case at the 16% usage rate) produced the
smallest observed MDD values of the gum acacia-based emul-
sions. Additionally, PG2000 yielded the smallest MDD of all
starch products tested, being statistically similar to that of A.
senegal (P < 0.05). The emulsifiers giving the very low initial
MDDs likely did so due to their relatively high affinity for the
Miglyol phase thereby rapidly moving to the interface and limiting
coalescence.
All of the emulsions were relatively stable over 3 d of storage at
22 ◦ C; however, the MDD of the starch-emulsified products did
increase slightly over time at both temperatures (see Figure 7).
In contrast, storage of the gum acacia emulsions at the
higher temperature had little effect on the MDD (data not
shown).
Miglyol-based beverages. Similar to the results observed in
the case of orange terpene-based beverages, in some samples the
measured MDD values of Miglyol-based beverages decreased dur-
ing storage. For example, Mira Mist and Bev101 exhibited this
behavior, as shown in Figure 8. Again, as discussed earlier, we do
not have a definitive explanation for this finding.
The initial MDD for the Mira Mist beverage was the largest
at 2.30 μm, with the rest of the emulsifiers producing bever-
ages having MDD values ranging from 0.89 μm to 1.49 μm at
22 ◦ C. The MDDs of the emulsions in beverages stored at
35 ◦ C were very similar to those stored at 22 ◦ C (data not shown).
Overall, Eficacia (at the 16% usage rate) was the only emulsifier
that produced an emulsion with an MDD of <1 μm. In addition,
PG 2000 had a surprisingly small MDD, being larger only than
Eficacia (16% usage level) and A. senegal and with a mean value
statistically similar to the latter.
The initial SDs (of particle size distributions) of both the Miglyol
concentrates and beverages ranged from 0.20 for Eficacia (16%
usage level) to 2.20 for Mira Mist illustrating the dispersion in
the particle size distribution of these emulsions. The distributions
were wider overall compared to those of the orange terpene-based
emulsions presented earlier in this article. As shown earlier, Eficacia
(at 16%) had the smallest MDD for both the Miglyol emulsions and
beverages; it also had the narrowest distribution (<0.13), which
demonstrates that it is likely the emulsifier to produce the most
stable emulsions.
Indication of long-term stability based on the initial
MDD. In the industry, MDD is commonly determined after
manufacturing to predict emulsion stability. While we recognize
that MDD is not an infallible predictor of long-term emulsion
stability, we suggest how these different emulsifiers may affect the
stability of cloud emulsions based on the MDD they produce.
For the orange terpene-based emulsions, Bev101, PG 1773, and
Mira Mist (Figure 9) produced the largest initial MDDs. Looking
at the results from the storage study, these are the 3 emulsions that
increased the most in MDD during storage in concentrated form.
Emulsifier performance (based on MDD) is similar for Miglyol
(see Figure 10) although the absolute values (MDD) are slightly
higher. The major difference in Miglyol-based emulsions is that
although PG 2000 was the 3rd smallest, it increased slightly over
time as discussed earlier. Ticamulsion (7% usage level) also appears
to have a larger MDD in Miglyol-based emulsions, but it remained
at that same size throughout the 3-d storage period.
Changes in turbidity
Orange terpene-based emulsions in beverages. Over the
decreased in turbidity (measured at 400 nm) at both temperatures,
Stability of beverage cloud emulsions . . .

indicating emulsion instability. However, A. senegal, Bev101, and
Eficacia (at both 7% and 16% usage rates) were more turbid
initially and throughout storage compared with the starches and
also compared with Ticamulsion (used at 7% or 16%) as indi-
cated in Figure 11. Such differences in turbidity reflect the greater
or smaller MDD values of these emulsions. Dluzewska and oth-
ers (2005) previously noted that gum acacia was able to form
beverages with higher turbidity than those based on modified
starch. Although Ticamulsion beverages (at both usage levels)
had very small MDDs, which were stable during storage, they
were less cloudy overall in comparison to the other gum acacia
products.
Miglyol-based emulsions in beverages. In beverages made
using Miglyol-based cloud emulsions, there was little change in
overall turbidity at either storage temperature (see Figure 12). This
to be fairly constant over time and not greatly affected by an
increase in temperature.
Visual observations of ringing
Orange terpene-based emulsions and beverages. At
22 ◦ C, ringing appeared in the Mira Mist, Eficacia (7% usage level),
and Ticamulsion (7%) concentrated emulsions after 2 wk of stor-
age. However, none of the other emulsion concentrates showed
ringing. At 35 ◦ C, Eficacia (7%), Ticamulsion (7%), Bev101, and
Mira Mist all showed ringing in the concentrates. The ring ap-
peared in the Mira Mist emulsion concentrate after just 1 wk
of storage, while rings appeared in the case of Eficacia (7%) and
Ticamulsion (7%) by week 2 and for Bev101 (3rd) by week 3.
Interestingly, the MDD data for these concentrates would not

E: Food Engineering &

turns out to be consistent with our previous work (Reineccius and have predicted this order of ringing (Figure 9). The Mira Mist

Physical Properties
Reiner 2008) that found the turbidity of Miglyol-based emulsions had the largest MDD, Bev101 had the 3rd largest, Ticamulsion

2.2 Mira Mist 35°C Figure 7–Effect of temperature on the MDD of

Mira Mist 22°C starch-based emulsion concentrates (Miglyol)
PG1773 35°C over 3 d of storage.
2.0
PG1773 22°C
PG2000 35°C
Mean Droplet Diameter, MDD (um)

1.8
PG2000 22°C

1.6

1.4

1.2

1.0

0.8

0.6
0 1 2 3 4
Days of Storage

A. senegal Figure 8–MDD of beverages prepared with

2.3
Efic 7% Miglyol-based emulsions over 4 wk of storage
Efic 16% at 22 ◦ C. Series with different letters denote
2.1 f Tica 7% significant differences between samples at
Tica 16%
week 4 (P < 0.05). Note: bcd = Ticamulsion
16% and Bev101.
Mean Droplet Diameter, MDD (um)

1.9 Bev101
PG1773
PG2000
1.7
Mira Mist

1.5
e

1.3 de
cd
bcd
1.1
bc
ab
0.9
a

0.7
0 1 2 3 4 5
Weeks of Storage

Vol. 75, Nr. 5, 2010 r Journal of Food Science E243

 Stability of beverage cloud emulsions . . .
(7%) had the 5th largest, and Eficacia (7%) had the 7th largest
MDD.
No ringing was observed in the beverages, at either storage
temperature, irrespective of which hydrocolloid emulsifier was
used. It seems somewhat surprising that ringing was not observed
in the Mira Mist beverages, considering the very large MDD and
wide particle size distribution of this emulsion.
Miglyol-based emulsions and beverages. In general, the
rate of creaming in emulsions made using Miglyol was much
faster than in emulsions made using orange terpenes as core mate-
rial. This would not be expected based on the specific gravity of
Miglyol (0.94 to 0.95 g/cm3 ) being much closer to that of water
than is that of orange terpenes (typically 0.85 to 0.89 g/cm3 ).
However, the greater instability of Miglyol-based emulsions might
nonetheless be predicted based on their larger MDD values and
E: Food Engineering &
very broad particle size distributions.
Physical Properties
At 22 ◦ C, the only emulsion concentrate that did not form a ring
was that based on Eficacia (16%). (Note this emulsion concentrate
had the smallest MDD of all emulsion concentrates [Figure 10].)
E244 Journal of Food Science r Vol. 75, Nr. 5, 2010
However, at 35 ◦ C storage, even this system displayed a faint ring.
All other concentrates began forming rings between day 3 and
week 1 (at 22 ◦ C). At 35 ◦ C, ringing became evident even earlier,
with Eficacia (7%) and Ticamulsion (7%) actually forming rings on
day 1. Clearly, the emulsions were not very stable in concentrated
form to ringing, which most likely is due to their MDD values
being >1 μm in all samples except Eficacia (16%) and as noted
earlier, their broad particle size distributions.
By week 1, all Miglyol-based beverages had formed clearly vis-
ible rings in the neck of the bottle (see Figure 13). The beverage
containing the modified starch, PG 2000, yielded the thinnest
ring of all starches, which is likely the result of having the smallest
MDD (of the starches, Figure 8) and a tighter particle distribution
(no particles >3 um) than the other starch products (substantial
proportion of particles up to 10 um) (see Figure 14). Interestingly,
the apparent thickness of the ring in the beverage corresponded
more or less to the thickness of the ring in the concentrated emul-
sion. For example, Mira Mist gave the thickest ring in both cases
and had the largest MDD and broadest particle size distribution
Figure 9–MDD of orange terpene-based
emulsion concentrates at T = 0.
Figure 10–MDD of Miglyol-based emulsion
concentrates at T = 0.
Stability of beverage cloud emulsions . . .

(Figure 14, bottom), while Eficacia (16%) produced a very thin
ring in the beverage at either storage temperature. (Note the Efi-
cacia 16% had the smallest MDD of all emulsifiers and a tight
particle size distribution.) A. senegal also yielded a thin ring in
the beverage (2nd smallest MDD), although the ring formed in
the concentrate was thicker than in the case of the Eficacia (16%)
concentrate. Overall, Eficacia (16% usage level) appeared to be the
most effective emulsifier for controlling creaming in Miglyol-based
emulsions.
Conclusions
For all of the emulsions studied, physical stability was found
to depend not only on the specific emulsifier employed, but also
on the type of oil used as core material. The MDD of emulsions
made with orange oil terpenes was consistently smaller than in the
case of emulsions made using MCTs (Miglyol). The result of larger
MDD was evidenced by the occurrence of creaming in all Miglyol-
based beverages. Overall, however, results showed that all gum
acacia products investigated yielded superior emulsion stability in

Bev101 Figure 11–Changes in turbidity occurring in

0.90
Efic 7% beverages containing orange terpene-based
A. senegal clouds over 4 wk of storage at 22 ◦ C.
0.85
Efic 16%
Tica 7%

E: Food Engineering &

0.80

Physical Properties
Tica 16%
PG1773
Absorbance at 400 nm

0.75 PG2000
Mira Mist
0.70

0.65

0.60

0.55

0.50

0.45
0 1 2 3 4 5
Weeks of Storage

A. senegal Figure 12–Changes in turbidity occurring in

0.90 Efic 7% beverages containing Miglyol-based clouds
Efic 16% over 4 wk of storage at 22 ◦ C.
0.85 Tica 7%
Tica 16%
0.80 Bev101
PG1773
Absorbance at 400 nm

0.75 PG2000
Mira Mist
0.70

0.65

0.60

0.55

0.50

0.45
0 1 2 3 4 5
Weeks of Storage

Figure 13–Ringing observed in Miglyol-based

beverages stored at 22 ◦ C. Left to right: A.
senegal, Eficacia 7%, Eficacia 16%, Ticamulsion
7%, Ticamulsion 16%, Bev101, Purity Gum
1773, Purity Gum 2000, and Mira Mist.

Vol. 75, Nr. 5, 2010 r Journal of Food Science E245

 Stability of beverage cloud emulsions . . .
E: Food Engineering &
Physical Properties
Figure 14–Typical particle size distributions of 4-wk-old Miglyol-based
beverages (22 ◦ C) (top: Purity Gum 1773; middle: Purity Gum 2000; bottom:
Mira Mist).
comparison to that achieved using the modified starches. Eficacia
(at a usage rate of 16%) and A. senegal were the best perform-
ing gum acacias in both oil systems. Of the 2 modified starches
examined, Purity Gum 2000 was the better performer. It is note-
worthy that Eficacia and Ticamulsion offered better performance
when used at 16% in both emulsion concentrates and beverages
compared with their recommended 7% usage level.
Acknowledgments
We thank TIC Gums, Inc. (Belcamp, Md., U.S.A.), Natl. Starch
Corp. (Bridgewater, N.J., U.S.A.), Tate & Lyle (Decatur, Ill.,
E246 Journal of Food Science r Vol. 75, Nr. 5, 2010
U.S.A.), and Colloides Naturels Intl. (Bridgewater, N.J., U.S.A.)
for their generous gifts of emulsifiers. Finally, we thank the officers
of Robertet Flavors, Inc. for permission to publish this work.
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