Innovative Food Science and Emerging Technologies 6 (2005) 107 – 114

www.elsevier.com/locate/ifset

Influence of emulsion and powder size on the stability of

encapsulated d-limonene by spray drying
Apinan Soottitantawata, Fanny Bigeardb, Hidefumi Yoshiia, Takeshi Furutaa,*,
Masaaki Ohkawarac, Pekka Linkod
a
Department of Biotechnology, Tottori University, 4-101, Minami, Koyama, Tottori, 680-8552, Japan
b
ENSBANA, Universite de Bourgogne, Dijon, France
c
Ohkawara Kakouki Co. Ltd., Yokohama 224-0053, Japan
d
Department of Chemical Technology, Helsinki University of Technology, P.O. Box 6100 HUT, Espoo, Finland

Received 20 August 2004; accepted 29 September 2004

Abstract

The microencapsulation of d-limonene by spray drying was investigated with respect to the effects of emulsion droplet size, powder
particle size, as well as to the effects of various kinds of matrices (gum arabic, maltodextrin, and modified starch) on its stability. It was
realized by studying release characteristics and oxidative stability during storage. The release and the oxidation decreased deeply with an
increase in powder and emulsion particle size for gum arabic and maltodextrin materials. Further, the distributions of emulsion size in the
powder showed an increase in the fraction of large emulsion droplets and changed to a bimodal distribution. However, the modified starch
HI-CAP 100 showed a higher stability of encapsulated d-limonene than the others. The influence of powder and emulsion size on its
encapsulated flavor as well as the change in the emulsion size during storage could not be observed.
D 2004 Elsevier Ltd. All rights reserved.

Keywords: Microencapsulation; Spray drying; Release; Oxidation stability

Industrial relevance: Spray drying is a common and useful unit operation for microencapsulation of food ingredients. Data on emulsion droplet size and on
powder size on product stability provide conflicting results which makes a systematic study regarding these factors highly relevant. The data suggest that an
optimal size of flavour powder should be selected for high retention during spray drying, stability during storage and for the ability to control release of flavour.

1. Introduction flavors during food processing and storage. The most

Microencapsulation of flavors is of great importance in
the flavoring and food industries. This is a technique of
encapsulation of flavors in liquid form in a carrier matrix in
order to obtain a dry flavor powder, which is easy to handle
because of the solid state. The capsules (5–300 Am in
diameter) can be made of sugars, gums, proteins, poly-
saccharides, lipids and synthetic polymers. The advantages
of this technology are not only in providing protection
against degradative reactions and preventing the loss of
flavor, but also in giving the controlled release function of
* Corresponding author. Tel.: +81 857 315273; fax: +81 857 31 0881.
E-mail address: takeshi@bio.tottori-u.ac.jp (T. Furuta).
1466-8564/$ - see front matter D 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ifset.2004.09.003
common way to realize the microencapsulation of flavors
is spray drying, which is the transformation of a feed from a
fluid state (solution, dispersion, emulsion) to dried partic-
ulate form. Spray drying is divided into different steps:
atomization, mixing of sprayed liquid and air, evaporation
of water and separation of product. Before spray drying, one
more step is necessary to transform feed liquid into powder:
emulsification of flavors into small emulsion droplets within
a carrier solution (O/W emulsion) by a homogenizer. Then
the emulsion is fed into the spray dryer and transformed into
droplets by an atomizer, followed by dehydrating in a hot
air. Numerous studies have been conducted to evaluate the
retention of flavor during spray drying and the shelf life of
the spray-dried powder.
108 A. Soottitantawat et al. / Innovative Food Science and Emerging Technologies 6 (2005) 107–114

Recently, Soottitantawat, Yoshii, Furuta, Ohkawara, and 2. Materials and methods

Linko (2003) has reported the influence of emulsion size on
the retention during spray drying of soluble and insoluble 2.1. Materials
flavor. The smaller emulsion size showed the higher retention
than the large emulsion size especially for the insoluble d-Limonene and gum arabic (GA) were purchased from
flavor. On the other hand, the retention had a maximum at the Nacalai Tesque (Kyoto, Japan). Maltodextrin with ca. 20 DE
optimum value of a mean emulsion size for the soluble flavor. (MD, Amycol No.1) and modified starch (HI-CAP 100) were
Further, they also reported small droplets of flavor embedded obtained from Nippon Starch Chemicals (Osaka, Japan) and
in the shell of the wall matrix inside the powder, confirming National NSC (Tokyo, Japan), respectively. The organic
the observations by other researchers (Chang, Scire, & chemicals used in the analyses were of analytical grade.
Jacobs, 1988; Finney, Buffo, & Reineccius, 2002; Kim &
Morr, 1996; Reineccius, Ward, Whorton, & Andon, 1995; 2.2. Preparation of encapsulated d-limonene spray-dried
Rosenberg & Young, 1993; Sheu & Rosenberg, 1995). In powder
addition, the stability and release characteristics of encapsu-
lated flavors from the powder are important for estimating the The carrier solution was prepared by dissolving the solid
shelf life of the flavor, as well as for the controlled release powders in warm distilled water. The carrier solution was
applications in food (Anandaraman & Reineccius, 1986; composed of 20% w/w GA or 20% w/w HI-CAP 100 or the
Bertolini, Siani & Grosso, 2001; Soottitantawat et al., 2004; mixture of 10% w/w of GA and 10% w/w of additive wall
Whorton, 1995; Whorton & Reineccius, 1995; Yoshii et al., materials MD. Then d-limonene was added to the solution as
2001). The wall materials still present a limited capacity model flavor. In an attempt to create different particle sizes of
against oxidation, since the most wall materials used act as emulsion, the mass ratio of amount of d-limonene to
semipermeable membranes. emulsifier, and the ways of the homogenization were
Concerning to the study on the effect of the emulsion controlled as shown in Fig. 1. A low solid concentration was
size on the shelf life of encapsulated orange oil flavor, used because it was easier to control the size of emulsion. To
Risch and Reineccius (1988) showed a longer shelf life of prepare emulsion of large droplet size (LE), d-limonene was
larger feed emulsion size. However, in the same manner added to the solution at the mass ratio to emulsifier (GA or HI-
for the shelf life of encapsulated fatty acid, Ishido, CAP 100) of 3:1 and then homogenized by using a Polytron
Hakamata, Minemoto, Adachi, and Matsuno (2002) has homogenizer (PT-10, Kinematica, Littau, Switzerland) at dial 8
recently reported a lower oxidation rate of linoleic acid for 3 min. Then, the remaining carrier solution was added to the
encapsulated in maltodextrin for the smaller size of feed emulsion to make up the mass ratio of the amount of d-
emulsion. According to these contrasting views, data limonene to the total wall materials to 1:4. On the other hand, to
concerning the influence of emulsion size on the shelf
life of product are scare and somewhat confusing. The
opposite was also reported in the case of emulsion liquid
(Lethuaut, Métro, & Genoi, 2002) which was explained by
the large surface area for the small emulsion size resulting
in the higher oxidation. On the other hand, the number of
lipid molecules per small droplet also decreases and the
amount of surface-active compounds adsorbed at the
interface might be increased. This limits initiation and
propagation resulting in the lower oxidation. In the same
manner, the effect of emulsion size on the encapsulated
flavor in the matrix could be explained. However, other
factors also should affect the shelf life of encapsulated
flavors. As Chang et al. (1988) reported on the effect of
the powder particle size, the larger size exhibited a more
protective effect against oxidation. From theses points, the
powder morphology and the arrangement as well as the
size of emulsion droplets inside the shell of the powder
seem to be important for the stability of the encapsulated
flavors.
Therefore, the objective of this work was to evaluate the
influence of emulsion droplet size and the powder size on
the stability of the encapsulated d-limonene. The morphol-
ogy of the powder and the changing of emulsion droplet size
during storage were also investigated. Fig. 1. Schematic procedure for creating small and large size emulsion.
 A. Soottitantawat et al. / Innovative Food Science and Emerging Technologies 6 (2005) 107–114
make a smaller emulsion droplet (SE), d-limonene was added
to the carrier solution to produce a flavor mass ratio to wall
materials of 1–4. The mixture was homogenized by using a
Polytron homogenizer (PT-6100, Kinematica) at 8000 rpm for
3 min and then passed through the Microfluidizer (model 110T,
Microfluidics, Newton, MA) at 12,000 psig (82.8 MPa). To
transform to the powder, the emulsion was spray dried in an
Ohkawara-L8 spray dryer (Ohkawara Kakouki, Yokohama,
Japan) as describe in the previous work (Soottitantawat et al.,
2003, 2004; Yoshii et al., 2001). The operational conditions of
the spray drying were: air inlet temperature of 200 8C, air outlet
temperature of 110F10 8C, feed rate of 45 mL/min and air flow
rate of 110 kg/h. The rotational speed of the atomizer was
controlled at 10,000, 20,000, and 30,000 rev/min to produce
the large powder (LP), medium powder (MP), and small
powder (SP), respectively.
2.3. Emulsion droplet size analysis
d-Limonene droplet size distribution of the feed liquid
emulsions were analyzed using a laser scattering particle size
analyzer (SALD-3000A, Shimadzu, Kyoto, Japan). At the
point of the measurement, the emulsion was further diluted to
less than 0.02% w/w to prevent multiple scattering effects.
The drop size distribution was expressed as volume
distribution and defined as the average emulsion size, D 43
(McClements, 1999; Soottitantawat et al., 2003). The specific
surface area, SSA, was calculated with the volume-surface
average emulsion diameter, D 32 (Linarès, Larré, & Popineau,
2001; McClements, 1999)
P P
zi D4i z D3 6
D43 ¼ Pi 3
; D 32 ¼ Pi i i2 ; SSA ¼
z D
i i i z D
i i i D32
where D 43 is the average emulsion size, D 32 is the volume-
surface average emulsion diameter, z i is the number of
droplets of diameter D i , and SSA is the specific surface area.
Each sample was analyzed in duplicate, and the data were
presented as an average.
d-Limonene droplet size in the powder after spray drying
was measured from the reconstituted emulsion. The powder
was reconstituted to 10% w/w of encapsulated powder by
dissolving 0.2 g of powder in 1.8 ml of distilled water at a
room temperature with a magnetic stirrer for 30 min.
Subsequently, the distribution of emulsion droplet were
measured in the same manner as above.
2.4. Powder particle size analysis
The size distribution of the spray-dried powders was
determined by dispersing them in 2-methyl-1-propanol and
analyzing by the laser light scattering method with a batch
cell unit (SALD-2000A, Shimadzu). The average particle
size and the specific surface area were reported as explained
above. Each sample was analyzed in duplicate and the data
were reported as an average.
109
2.5. Surface oil determination
The method for determining the surface oil content was
explained in the previous work (Soottitantawat et al.,
2003). One tenth of a gram of powder was washed in 2 ml
of hexane containing the internal standard cyclohexanone,
1 Al/ml, in a glass bottle. The mixtures were slowly mixed
on a rotary shaker for the optimum time of 30 s at ambient
temperature. The solvent was then filtered. d-Limonene
content in the organic phase was measured by gas
chromatography. The results were the average of the
duplicates in each sample.
2.6. Morphological characterization by scanning electron
microscopy (SEM)
The external and internal structure of the encapsulated
powder were studied by SEM (JSM 5800, JEOL, Tokyo,
Japan). The powders were placed on the SEM stubs using a
two-sided adhesive tape (Nisshin EM, Tokyo, Japan) and
then analyzed at 15 kV acceleration voltage after Pt–Pd
sputtering by MSP-1S magnetron sputter coater (Vacuum
Device, Tokyo, Japan). The internal structure was inves-
tigated as described in our previous work (Soottitantawat et
al., 2003).
2.7. The stability of spray-dried d-limonene
The stability of encapsulated d-limonene was defined as
the release and the oxidation of d-limonene as reported in
our previous work (Soottitantawat et al., 2004). About 0.1 g
of the spray-dried powder was weighed and spread as a thin
layer in a 15 ml (20f48 mm) glass bottle, and stored in a
51F5% RH and 50 8C desiccator. At this condition the
highest release and oxidation rate were observed (Sootti-
tantawat et al., 2004) without the change of external
structure of the particles, since it is close to the glass
transition point of the capsule matrices. Fifteen sample
bottles were placed in a desiccator to study the release and
oxidation kinetics for 25 or 30 days. At fixed time intervals,
the bottles were removed from the desiccator in order to
extract and measure the residual amounts of d-limonene and
the oxide compounds by heat extraction method as
described in our previous work (Soottitantawat et al.,
2004). The retention of d-limonene was defined as the
ratio of the remaining amount of d-limonene to the initial
one. The amount of the oxide compound was expressed by
the mass ratio of the oxide to the retained d-limonene.
Avrami’s equation (Weibull distribution function), was
applied to the release time-courses of the encapsulated d-
limonene as reported in the previous work (Soottitantawat et
al., 2004; Yoshii et al., 2001).
R ¼ exp½  ðkt Þn 
where R is the retention of d-limonene, t is the storage time,
k is the release rate constant, and n is a parameter
110 A. Soottitantawat et al. / Innovative Food Science and Emerging Technologies 6 (2005) 107–114

Table 1
Properties of encapsulated d-limonene after spray drying
Type of Samplea Emulsion Reconstituted SSA of reconstituted Powder SSA of Retention during Surface
carrier solid size (Am) emulsion (Am) emulsion (m2/m3) size (Am) powder (m2/m3) spray drying (%) oil (%)
GA LELP 3.16 3.42 3.16 70 0.10 82 3.19
LEMP 2.91 2.83 3.10 51 0.17 97 6.81
LESP 3.01 2.53 3.37 31 0.66 95 5.96
SELP 0.81 1.14 6.08 61 0.12 99 1.06
SEMP 0.80 0.86 7.88 54 0.16 99 2.75
SESP 0.80 0.90 7.69 32 0.43 99 2.89
GA and LELP 3.37 4.09 3.27 65 0.11 95 0.72
MD (1:1) LEMP 3.26 2.97 3.39 47 0.19 91 0.56
LESP 3.20 2.87 3.33 24 0.95 87 0.45
SELP 0.84 0.84 7.88 60 0.12 100 0.44
SEMP 0.90 1.19 5.74 46 0.20 98 0.68
SESP 1.04 1.73 4.28 27 0.68 93 0.72
HI-CAP 100 LELP 2.12 2.16 3.24 60 0.12 79 1.25
LEMP 2.38 1.95 3.69 35 0.26 74 0.63
LESP 2.10 1.60 4.42 23 0.37 80 1.28
SELP 0.66 0.69 9.50 57 0.13 94 0.43
SEMP 0.68 0.71 9.00 38 0.25 92 0.39
SESP 0.67 0.70 9.17 23 0.36 89 0.46
a
LE: large emulsion size, SE: small emulsion size, LP: large powder size, MP: medium powder size, SP: small powder size.

representing the release mechanism. Furthermore, since the
amount of limonene oxide and carvone increased linearly
with time during the initial period, the apparent oxidation
rate constants were calculated on the basis of the zero order
kinetic reaction scheme (Soottitantawat et al., 2004). In
addition, the changes of emulsion droplets in the powder
during storage were also investigated. The encapsulated d-
limonene powders were reconstituted and the size was
measured as described above.
3. Results and discussion
3.1. The physical properties and the surface oil content of
the spray-dried powder
Six types of the spray-dried powders for each carrier
solution were prepared in various combinations of the
emulsion size and the powder size, in order to investigate
the effects on the stability of d-limonene during storage.
The small powder size (25–30 Am: SP), medium powder
size (40–50 Am: MP) and large powder size (60–70 Am: LP)
were prepared by controlling the rotational speed of
atomizer at 10,000, 20,000, and 30,000 rpm, respectively.
Two types of the reconstituted emulsion size were catego-
rized as a large emulsion (2.5–4 Am: LE) and a small
emulsion (~1 Am: SE). The physical properties of the spray-
dried d-limonene powders, such as the reconstituted
emulsion size, powder size, the surface oil content, and
the flavor retention were shown in Table 1.
d-Limonene retention during spray drying was defined
as the ratio of the d-limonene in the powder to the 0.25 kg
d-limonene/kg dried solid of the feed emulsion. Flavor
retention in all systems was higher than 80%. In all wall
material systems of powder size as controlled with the
rotational speed of atomizer seemed to have a less important
effect on the flavor retention, as compared to the influence
of emulsion size as shown in Table 1. As mentioned by
Chang et al. (1988), the large atomized droplets have
reduced surface area to volume ratio which would result in
better d-limonene retention, but it also takes a longer time
for film formation around the large atomized droplets in the
drying process. The longer was the time necessary for the
film formation, the greater was the loss of volatile flavors.

Fig. 2. External structure of encapsulated d-limonene powder for the small powder of about 30 Am and the small emulsion of about 1 Am. Wall materials: (a)
GA, (b) Blend GA-MD, (c) HICAP-100.
 A. Soottitantawat et al. / Innovative Food Science and Emerging Technologies 6 (2005) 107–114 111

observed for the GA wall material systems. The larger

emulsion size showed a higher surface oil content than the
smaller emulsion, as reported by Soottitantawat et al.
(2003). However, no important effects on the surface oil
content were found in the powder size to the surface oil
content.
The outer structure of encapsulated d-limonene powders
in the wall materials, GA, blend GA-MD, and HICAP 100
are shown in Fig. 2a, b, and c, respectively. Both groove and
smooth powder surfaces were observed. However, the
smooth surface of powder was observed more in the HI-
CAP 100 wall materials than with the others.

3.2. Effect of the powder particles size on stability of

encapsulated flavor powder

In the previous works (Soottitantawat et al., 2004), the

stability of encapsulated d-limonene was indicated by using

Fig. 3. Effect of powder and reconstituted emulsion size on the parameters

of Avrami’s equation for the d-limonene encapsulated powder stored at
51% RH and 50 8C. (a) Release rate constant, k, (b) release mechanism
factor, n. o., GA; 5n, blend of GA-MD; DE, HI-CAP 100. Filled
symbols represent a large reconstituted emulsion and unfilled symbols for a
small reconstituted emulsion. The error bars indicate 95% confidence level.

The flavor retention is higher for the small emulsion than

large emulsion. As described in our previous work
(Soottitantawat et al., 2003), the evaporation of flavor
seems to be easier with large emulsion size during atom-
ization. The larger emulsion droplets were sheared into
smaller droplets. Wall materials of GA and modified starch
HI-CAP 100, which have good emulsifier properties,
showed no important effects on the flavor retention in the
comparison to the effect of the emulsion size. GA showed a
higher flavor retention at the same size of emulsion droplets
when compare to other wall materials. Even though, HI-
CAP 100 was easier to use in order to make fine emulsion
droplets. Fig. 4. Effect of powder and reconstituted emulsion size on the formation
rate constant of the d-limonene encapsulated powder stored at 51% RH and
The retaining of d-limonene on the powder surface
50 8C. (a) Formation of limonene oxide, (b) formation of carvone. o., GA;
(percent of surface oil) was defined as the ratio of d- 5n, blend of GA-MD; DE, HI-CAP 100. Filled symbols represent a large
limonene on the surface to the total flavor in the powder. As reconstituted emulsion and unfilled symbols for a small reconstituted
shown in the Table 1, higher surface oil content was emulsion. The error bars indicate 95% confidence level.
112 A. Soottitantawat et al. / Innovative Food Science and Emerging Technologies 6 (2005) 107–114

Fig. 5. Change in distribution of reconstituted emulsion during storage at 51% RH and 50 8C for the small powders of about 30 Am and small emulsion size of
about 1 Am. Wall materials: (a) GA, (b) Blend GA-MD, (c) HI-CAP 100. 5, 0 day; o, 7 day; D, 14 day; q, 21 day; R , 28 day.

the release rate and the oxidation rate. Limonene oxide and
carvone were chosen as indicators of the oxidation. There-
fore, the release rate constant and release mechanisms
parameter were calculated by fitting the release time courses
of d-limonene as shown in Fig. 3 with the Avrami’s
equation as mentioned before in the function of powder size.
The apparent oxidation rate constant were also calculated by
using zero order kinetic reaction schemes fitting with the
formation time courses of limonene oxide and carvone as
shown in Fig. 4 against the powder size.
In Fig. 3a, when GA and blend GA-MD were used as
wall materials, the small powder size showed a higher
release rate constant than the large powder. The oxidation
rate constant also decreased with an increase in powder size
as shown in Fig. 4a and b. The larger size of encapsulated d-
limonene powder showed a longer product shelf life. This
can be explained by the reduced surface area to volume ratio
of the large powder as shown by the SSA values of powder
in the Table 1, resulting in the decrease in the effective
surface area for d-limonene to release and react with
oxygen. However, for HI-CAP 100 wall materials, the
effect of the powder size on the stability could not be
observed, particularly in the release rate constant. Further-
more, the lower release and the oxidation rate constants
were observed than with the GA or blend GA-MD as wall
materials. The higher stability of HI-CAP 100 might be a
result of the morphology during spray drying. As shown in
Fig. 2, the smooth surface area of HI-CAP 100 powders was
observed comparing to other wall materials. In the same
powder size, the effective surface area of the smooth surface
powder is lower than the groove surface powder resulting in
the lower release and oxidation rate of encapsulated d-
limonene. Further, it might also be a result of a unique
polymer structure of HI-CAP 100 with a dextrose equivalent
of 32–37 (National Starch and Chemical, 1999). Further-
more, in Fig. 3b, most of n values are in the range of 0.30–
0.80 which shows that the release should be controlled by
the diffusion mechanism. This agrees well with the results
of the previous work (Soottitantawat et al., 2004; Yoshii et
al., 2001).
In addition, the distribution and average reconstituted
emulsion size during storage were also measured to study
the stability of the encapsulated d-limonene as shown in
Figs. 5 and 6. In Fig. 5a and b, the change in the distribution
of reconstituted emulsion size was reported for GA and
blend GA-MD wall materials, respectively. The distribu-
tions showed an increase in the fraction of large emulsion
droplet and a change to a bimodal distribution. On the other
hands, the change in the distribution of emulsion size in HI-
CAP 100 could not be observed as shown in Fig. 5c. These

Fig. 6. Change in mean reconstituted emulsion size during storage at 51% RH and 50 8C for the small initial reconstituted emulsion size (SE) of about 1 Am.
Wall materials: (a) GA, (b) Blend GA-MD, (c) HI-CAP 100. 5, Small powder (SP); D, Medium powder (MP); o, Large powder (LP).
 A. Soottitantawat et al. / Innovative Food Science and Emerging Technologies 6 (2005) 107–114 113

results supported the higher stability of encapsulated d-

limonene in HI-CAP 100 wall materials than in the others as
explained above. The changes in average reconstituted
emulsion size were also investigated as a function of powder
size during storage in Fig. 6. In Fig. 6a and b, the smaller
powder size showed a higher emulsion size increasing rate
than the larger powder size for GA and blend GA-MD as
wall materials. These observations also agreed with the fact
that the large powders were shown to exhibit a better
protection against oxidation for the encapsulated d-limo-
nene. However, for HI-CAP 100, the change in average
reconstituted emulsion size for all powder sizes could not be
observed as also shown in Fig. 6c. These results agreed with
the powder size had almost no effect on the stability of
encapsulated d-limonene HI-CAP 100 powder. This is
likely to result from the high stability of encapsulated d-
limonene in HI-CAP 100, and could overcome the powder
size effect.
Furthermore, SEM was also used to the internal structure
of encapsulated d-limonene for the different powder sizes as
shown in Fig. 7 for GA with the large size emulsion. d-
Limonene droplets were located in the form of small
droplets embedded in the shell of wall matrix as shown in
Fig. 7a, b, and c. A thicker shell matrix was observed in the
large powder. On the other hand, for the small powder the
thinner shell matrix and the higher concentration of d-
limonene droplet were observed especially near the inner
and outer surface of the shell. d-Limonene droplet, located
near the surface of the powder, should be easier to release or
react with the outside oxygen. These observations could be
used to explain why the smaller powder showed a lower
stability in addition to the larger effective surface area of the
small powder.
3.3. Effect of the reconstituted emulsion size on stability of
encapsulated d -limonene powder
The effect of the reconstituted emulsion size on the
stability of encapsulated d-limonene was also studied as
shown in Figs. 3 and 4. The filled symbols represent a large
reconstituted emulsion and unfilled symbols represent a
small reconstitute emulsion. The small reconstituted emul-
sion size showed the higher release rate and oxidation rates
Fig. 8. Change in mean reconstituted emulsion size during storage at 51%
RH and 50 8C for the large initial reconstituted emulsion size (LE) of about
2 Am of HI-CAP 100 wall materials. 5, Small powder (SP); D, Medium
powder (MP); o, Large powder (LP).
constant than the larger emulsion size in the GA and blend
GA-MD wall materials. This indicates the larger size of d-
limonene in powder showed a longer shelf life of the
products. As mentioned above, this could be explained by
the higher effective surface area of the small emulsion
droplet to release and to react with the oxygen. The results
are in an agreement with those of Risch and Reineccius
(1988) but in a conflict with those of Ishido et al. (2002). As
mentioned by Lethuaut et al. (2002), the decrease of
oxidation rate of the small emulsion size should come from
the decrease of the lipid molecules and increase of surface
active compounds that could limit the initiation and
propagation of the chain reaction. From Ishido et al.
(2002), a fatty acid was used as core material of which
oxidation mechanism should be composed of the chain
reaction. That could explain the higher stability of smaller
emulsion droplet in the matrix materials. However, in Risch
and Reineccius (1988) and in the present work, d-limonene
was used as model flavor which has a zero order kinetic of
the oxidation reaction as mentioned in the materials and
methods section. The reaction is not dependent on the
concentration of the reactant d-limonene. Therefore, the
effective surface area should control the oxidation rate of

Fig. 7. Microstructure of encapsulated d-limonene powder when blend GA-MD was used as wall materials for the large reconstituted emulsion size (LE). (a)
Small powder (SP); (b) Medium powder (MP); (c) Large powder (LP).
114 A. Soottitantawat et al. / Innovative Food Science and Emerging Technologies 6 (2005) 107–114
encapsulated d-limonene in the wall matrix. The calculated
surface area, SSA, of the small emulsion size is 2 times
larger than the large emulsion size as shown in Table 1. That
is why the higher stability of large reconstituted emulsion
droplet was reported.
However, for HI-CAP 100, the effect of the emulsion
size on the stability could not be observed. These results
also agreed with the unchanged of mean reconstituted
emulsion size during storage in both case of a small
emulsion size and large emulsion size as shown in Figs.
6c and 8, respectively. These should be from the high
stability of encapsulated d-limonene in HI-CAP 100 as
discussed above, which can overcome the effect of emulsion
droplet size.
4. Conclusions
The powder size showed the influence on the stability of
the encapsulated flavor in addition to the powder properties
such as the bulk volume and the flowability of powder. The
powder size distribution from the spray drying could be
effectively controlled by changing the rotational speed of
the centrifugal atomizer. The large powder size showed the
higher stability and lower release of encapsulated flavor
than the small powder size. Furthermore, in addition to the
effect of emulsion droplet size on the retention during spray
drying (Soottitantawat et al., 2003), the emulsion size also
affected to the stability of encapsulated flavor powder. The
small flavor size in the powder showed the lower stability
than the large size of flavor especially for the simple zero
order kinetic oxidation of flavor (d-limonene), even though
the smaller size of emulsion can give the higher retention
during the spray drying (Soottitantawat et al., 2003).
Therefore, the optimal size of flavor in the powder should
be recommended for both of the high retention during spray
drying and its stability during storage as well as the ability
to control the release of flavor.
Acknowledgements
This study was partly supported by the Grant-in-Aid for
Scientific Research (No. 15580108) from the Ministry of
Education, Science, and Culture of Japan. We also acknowl-
edge Nippon NSC (Tokyo, Japan) and Nippon Starch
Chemicals (Osaka, Japan) for their kind gift of HI-CAP
100 and MD, respectively.
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