ENGINEERING/PROCESSING
Comparison of Spray-drying, Drum-drying
and Freeze-drying for b-Carotene
Encapsulation and Preservation
STEPHANE A. DESOBRY, FLAVIA M. NETTO and THEODORE P. LABUZA
ABSTRACT
Pure b -carotene was encapsulated in 25 Dextrose Equiva-
lent maltodextrin by three drying processes (spray, freeze
and drum). Stability was studied at 11% and 32% RH and 25°C,
35°C and 45°C. No significant influence of %RH was observed
on the retention of b -carotene. Oxidation followed first order
kinetics with an initial fast first order reaction followed by a
second much slower first order reaction period. Although
drum-drying caused more initial loss in drying, the lower
surface carotenoids and larger particle size resulted in greater
stability as compared to the other methods. The chromamet-
ric measurements of “L” and “a” corresponded to the other
kinetics and indicated that the first period rapid loss corre-
sponded to the oxidation of surface carotenoids.
Key Words: carotenoids, encapsulation, oxidation, stabil-
ity kinetics
INTRODUCTION
VITAMIN A IS THE MOST COMMON DIETARY DEFICIENCY IN THE
world (Simon, 1990). b-carotene theoretically possesses 100% vita-
min A activity and provides 80% of vitamin A value of fruit and
vegetables (Chou and Breene, 1972; Chen et al. 1995), while a-car-
otene possesses only 52 2% of vitamin A activity (Bushway and
Wilson, 1982; Heinoven, 1990). Moreover, the demand for b-caro-
tene has increased due to reported anticancer activity and other health
benefits (Sims et al., 1993). It is implicated as an anticancer com-
pound (Halter, 1989, Ziegler, 1989), free radical quencher and bio-
logical antioxidant (Bendich and Olson, 1989; Krimsky, 1989). How-
ever, b-carotene is sensitive to oxidation during storage and Wagner
and Warthesen (1995) found a half-life of 2–3 days at 23°C in spray-
dried carrot juice.
Encapsulation entraps a sensitive ingredient, e.g. b-carotene in a
coating material or “wall”, which functions to isolate the ingredient
from the environment. The simplest means of encapsulation is to
emulsify the sensitive ingredient (usually an oil) in a solution con-
taining the wall material followed by drying such that the wall mate-
rial then coats or entraps the oil matrix within it providing a barrier
to oxygen and water vapor. The dry material forms either as a pow-
der as in spray-drying as a solid which can be ground to different
particle sizes (as with freeze-dried coffee). Spray-drying is the most
common method of drying encapsulation as the cost of drying is 30
to 50 times less than freeze-drying which is used in the flavor indus-
try. Spray-drying provides a very large surface area which enhances
oxidation, if the wall material is not thick or dense enough to pro-
vide a good oxygen barrier. Generally the wall must comprise at
least 80% of the total weight which reduces product delivery effi-
ciency (Moreau and Rosenberg, 1996).
Stability is influenced by the composition of the wall (Moreau
Author Desobry is with the Laboratoire de Physico-chimie et Genie Alimentaires,
ENSAIA-INPL, 2 Avenue de la Foret de Haye, 54500 Vandoeuvre, France. Au-
thor Netto is with Faculdade de Engenharia de Alimentos - Universidade Estadual
de Campinas, Campinas-SP CP 6121, 13083-970, Brazil. Author Labuza is with
the Dept. of Food Science & Nutrition, Univ. of Minnesota, 1334 Eckles Ave.,
Saint-Paul, MN, 55108. Address inquiries to Dr. T.P. Labuza.
1158 JOURNAL OF FOOD SCIENCE—Volume 62, No. 6, 1997
97-0377-Desobry & Netto & Labuza.p65 1158
and Rosenberg, 1996). Maltodextrins are a good compromise be-
tween cost and effectiveness, are bland in flavor, have low viscosity
at high solids ratio and are available in different average molecular
weights (DE values of 4, 10, 15, 20, 25, 30 and 42 with average
molecular weight decreasing as DE increases). This allows for blend-
ing to create different wall densities which provides protection against
oxidation of the encapsulated ingredient. Higher DE maltodextrins
form a more dense more oxygen impermeable matrix providing longer
shelf life for orange oil (Anandaraman and Reineccius, 1986) and
for b-carotene (Wagner and Warthesen, 1995). However, because of
the lowering of the glass transition temperature as molecular weight
decreases, the material has higher hygroscopicity and can cake (Chuy
and Labuza, 1994) destabilizing the product as the wall collapses.
Spray-drying, freeze-drying and drum-drying are processes with
different time temperature regimes and can lead to different stability
of products due to different wall thicknesses and densities. No one
has reported on the use of drum-drying for encapsulation. Our ob-
jective was to compare the effect of these three drying processes on
pure b-carotene encapsulated with 25 DE maltodextrin.
MATERIALS & METHODS
Encapsulation method
Mixture. Pure trans-b-carotene (0.5 g from Aldrich Chemical
Company, Milwaukee, WI) was added to 1000g of an aqueous solu-
tion of 40% maltodextrin 25 DE (Grain Processing Corporation,
Muscatine, IA). Because of the insolubility of b-carotene, to get a
homogeneous suspension before drying, 12L of the mixture was ho-
mogenized three times at 252.5 MPa in a Gaulin homogenizer 125E
(Everett, MA). Of this mixture, 4L were spray-dried, 4L were drum-
dried, and 4L were freeze-dried.
Spray-drying. The mixture was spray-dried in a Niro Utility
Model (Niro Atomizer Ltd., Columbia, MD). The dryer was operat-
ed at an air inlet of 170±5°C and outlet 95 ± 5°C. The wet bulb
temperature was about 43°C (air inlet = 50%RH)
Drum-drying. A double drum pilot-scale drier with counter ro-
tating drums (15 cm diameter @ 1.5 rpm) was fed with 1L/h of the
mixture between the rolls. Their diameter and speed were respec-
tively 15 cm and 1.5 rpm. The surface temperature was maintained
at 140°C giving a residence time of 45 sec. A sheet of maltodextrin
with encapsulated carotene was collected and ground through a 100
mesh screen to provide a powder.
Freeze-drying. The mixture was frozen at -35°C. The freeze dryer
Dura-top (FTS systems, Store Ridge, NY) was operated at a pres-
sure of 50 mtorr. The temperature was increased stepwise as follow:
24 hr @ -35°C, 18 hr at -15°C, 18 hr at -5°C, 18 hr at 0°C and finally
12 hr at 5°C. A dried mixture was obtained and ground as previously
to provide a powder.
Storage study. Samples for the zero time were analyzed within
24 hr after drying. For the storage test, Petri dishes (6 cm dia and 1.5
cm ht) were filled with the powder to allow for a high surface area
between air and powder during storage. Samples of each powder in
the dishes were stored in covered glass fish tanks (~ 73L) under the
following storage conditions: 25°C, 35°C and 45°C at 11% and 32%
RH using saturated salt solutions (LiCl2 and MgCl2 respectively).
Duplicate samples were used for each measurement. The coefficient
of variation never exceeded 2%.
12/3/97, 2:21 PM
 Carotene measurement
Total carotene. To measure the initial carotene content and caro-
tene retention during storage, 50 mg of powder was dispersed in 2.5
mL of water and 25 mL of hexane was added to a test tube (2.5 cm ×
10 cm). The tube was then sealed and agitated at 500 rpm, for 30
min on a G24 shaking table (New Brunswick Company inc., New
Brunswick, NJ). The yellow-to-orange color of the hexane fraction
was measured at 454 nm with a DU-20 spectrophotometer (Beck-
man, Irvine, CA, USA), according to Zhou et al. (1994).
Surface carotene. To determine surface carotene in the finished
powders, the methodology described by Wagner and Warthesen
(1995) was used. Triplicate samples (50 mg) of powder were weighed
into test tubes (diameter 2.5 cm × ht 10 cm) and extracted with 25
mL hexane. After 15 sec of shaking (100 rpm), the powder particles
were centrifuged at 1000 × g for 1 min and the carotene concentra-
tion in the supernatant was measured by spectrophotometry (454 nm).
The percentage of surface carotene was determined by dividing the
surface concentration by the total b-carotene concentration in the
powder.
Purity and isomerization. The purity and degree of isomeriza-
tion of the initial carotene and the initial amount of total carotene
and surface carotene after drying were also measured by HPLC. A
Vydac 201TP54 column (C18, 5 m particle size, 4.6 mm i.d.x 25 cm,
Vydac, Hesperia, CA) was used with a mobile phase of
acetonitrile:methanol:dichloromethane (60:36:4 v/v/v) at a flow rate
of 1 mL/min maintained by a Waters pump (Model M-6000 ; Waters Fig. 1–Water sorption isotherms of maltodextrin 25 DE with b-caro-
tene encapsulated by spray-drying , drum-drying , and freeze-
associates Inc., Milford, MA). Detection was with a Waters 401R drying at 45°C.
refractive index detector. No isomerization was found and HPLC
results confirmed the spectrophotometric results. For all storage tests
only the spectophotometric method was used.
mixed by hand with a spatula to make the sample homogeneous, and
Color transferred back to the dish for measurement.
A chromameter model D25-2 (Hunterlab, Fairfax, VI, USA) was
used to measure L, a, and b values of powders during storage. A Glass transition
sample stored in a the petri dish was transferred into a beaker and The glass transition temperature at 11% and 33 % RH was mea-

Table 1—Characteristics of maltodextrin-carotene powders

Drying % initial Tg value Tg value particle
process drying at 11% RH at size Solid Bulk Surface
loss 32% RH (µm) (%) Density Density Carotene
Spray 11% 69+1°C 46+1°C 30+10 1.52 + 0.03 0.817 + 0.008 38+2%
Drum 14% 71+1°C 48+1°C 105+15 1.34 + 0.03 0.699 + 0.008 24+2%
Freeze 8% 73+1°C 47+1°C 80+25 1.52 + 0.03 0.677 + 0.008 35+2%

Table 2—GAB moisture sorption isotherm parameters of spray-dried, drum-dried and freeze-dried b-carotene capsulated with malodextrin
Drying P value Standard GAB m0 aw at Qs
process (%) error (%) kb constant, C gH2O/gsolid monolayer cal/mol H2O (%)
Spray 4.87 0.05 1.15 3.86 0.061 0.293 853
Drum 6.34 0.06 1.15 3.44 0.062 0.304 781
Freeze 3.46 0.05 1.20 6.14 0.043 0.240 1147

Table 3—Arrhenius parameters (first order) and half-life values for b-carotene encapsulated with malodextrin 25 DE and stored at 32% RH
Retention Actual time Calculated total
of b- Storage Oxidation rate, Activation r2 of Calculated to 50% loss retention from
Drying tc carotene, timee k, at 25°C energy Arrhenius half-life at from zero original (before
process (wk) at tc (%) (wk) (wk)-1 (Kcal/mol) plot 25°C time (wk) drying) after 15 wk
Spray 11 38+2 t<tc 0.097 + 0.008a 14.19 0.95 7.1 6 27%
t>tc 0.026 + 0.004b 7.69 0.90 27.0
Drum 5 66+2 t<tc 0.082 + 0.008a 10.11 0.91 8.4 24 40%
t>tc 0.007 + 0.002c 9.80 0.94 98.2
Freeze 6 50+2 t<tc 0.110 + 0.008a 12.64 0.97 6.3 6 35%
t>tc 0.020 + 0.003d 8.74 0.98 34.5
a-d Same letters represent no significant difference at the 95% confidence level;
e tc designates when the 2nd first order period began.

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 Encapsulation for Carotene Preservation . . .

sured by DDSC with a DSC-7 (Perkin Elmer Company, Norwalk,

CT, USA). The temperature range was from 20°C to 100°C with a
heating rate of 5°C /min.
a
Powder density and particle size distribution
The densities of the powders were measured with an Air Com-
parison Pycnometer model 930 (Beckman, Fullerton, CA). The par-
ticle size distribution was determined with a Droplet and Particle
Sizer Series 2600c (Malvern, Worchester, England).

Water sorption isotherms (WSI)

WSI were determined by storage at 45°C over different saturated
salt solutions of specific equilibrium relative humidity (RH) for 3 wk.
The moisture content was measured by the Karl Fischer method.

RESULTS & DISCUSSION

THE THREE PROCESSES OF DEHYDRATING THE MALTODEXTRIN-
carotene mixture differed in the following ways. Freeze-drying oc-
curs at a low temperature from the frozen state avoiding any water
phase reactions and most oxidation because of the vacuum. During
drum-drying, the water boils off at 100°C and powder temperature
begins to rise above that as it rotates around during the short resi-
dence time of 45 sec. Since the melting point of the carotenoids is
around 193°C and the dryer surface is at 140°C it is doubtful that
any melting would occur. The higher temperature may cause the
malto-dextrin matrix to collapse, accelerating degradation, but the b
residence time was short. During spray-drying, particles dry at the
wet bulb (43°C) in 2–3 sec, but rises to the air outlet of 95°C, which
can result in reactions, but these should be less than in drum-drying.
Since the air inlet was 170°C, no melting of the carotenoid crystals
should take place.

Loss during drying

The drying and encapsulation process (Table 1) led to an 8% deg-
radation of b-carotene with freeze-drying, 11% with spray-drying
and 14% with drum-drying. Note that this was measured within 24
hr after drying. This range of carotene loss was expected based on
the above drying sequences. The loss in drum-drying, the highest
temperature process,was still within reason. In the following discus-
sion, these process losses were not considered and 100% retention
corresponds to the resultant amount of b-carotene in each powder
after drying.

Initial powder properties

The WSI of the spray-dried and drum-dried powders were simi-
lar while the freeze-dried absorbed less water (Fig. 1). The GAB
parameters (Table 2) were not very different between the spray-dried c
and drum-dried powder while the freeze-dried had a smaller mono-
layer (Table 1). The three processes also did not affect the glass tran-
sition temperature (Tg), as no differences were found between the
powders. Tg values at 11% RH and 32% RH were about 47°C and
71°C respectively (Table 1). Thus during the storage tests, the mate-
rials were all in the glassy state.
Average particle sizes and the solids and bulk densities of the
powders were also compared (Table 1). Some morphological and
dimensional differences resulted from the different encapsulation pro-
cesses. The spray-dried capsules were spherical as would be expect-
ed. The high ratio of surface/volume for a sphere and the large amount
of small spheres would favor oxidation of b-carotene. The drum-
and freeze-dried powders had complex forms because they were
ground after dehydration. Although they had the same wall/carotene
ratio, the larger particle provided a larger barrier against diffusion of
oxygen into the inner carotene and also had less surface carotene per
volume. However, with freeze-drying, the large pores extending into
the interior would allow for easy diffusion . The drum-dried powder
was very compact and formed into large pieces. The freeze-dried Fig. 2 –Storage stability of b-carotene encapsulated in a maltodex-
trin 25 DE by spray-drying (a), drum-drying (b), and freeze-drying
maltodextrin particles were more regular, thinner and smoother. The (c). Stored at 25°C , 35°C and 45°C at 11% RH and 32% RH.
smaller diameter of the spray-dried capsules should increase the ex-

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 change between oxygen and surface b-carotene as noted. The bulk
density differences would favor faster oxidation of freeze-dried since
it is the smallest, indicating the least collapse. a
The different encapsulation processes also affected the amount
of surface carotene which decreased as the particle size increased.
The drum-dried product provided the best encapsulation (Table 2)
with only 24±2% of surface carotene as compared to the spray-dried
at 38±2% and freeze-dried at 35±2%. Although the same grinding
process was used for the freeze-dried and drum-dried products, they
did provide for a different particle sizes, possibly due to different
cohesion forces set up when the dried matrix formed.

b-carotene retention during storage

The retention of carotene during storage was compared for the
three processes (Fig. 2). For all powders, the rate was faster at high-
er temperatures and 32% RH slightly accelerated b-carotene oxida-
tion during the first weeks of storage compared to 11% at 45°C. This
%RH difference was reduced with time and finally disappeared. Af-
ter 15 wk storage, drum-drying gave the best b-carotene preserva-
tion for all temperatures with at least 47±2% retention (Fig. 2-b)
during storage, retaining 40% of the original material. This better
retention was expected, based on particle size and surface carotenoid
content. Based on the smallest particle size and highest surface car-
otenoid content, the spray-dried powder showed the fastest degrada-
tion kinetics (Fig. 2-a). About 80±2% of the spray-dried b-carotene b
degraded in 7 wk at 45°C or in 12 wk at 35°C. After 12 wk at 25°C,
the carotene retention was 30±2%. Adding the 11% loss during dry-
ing, only 27% of the original carotene was retained. The freeze-dried
powder had a retention of about 38% after 15 wk (Fig. 2-c) and, with
the drying loss, about 35% of the initial carotene was retained, 5%
less than for the drum-dried product.
The degradation kinetics of encapsulated b-carotene initially fol-
lowed first order kinetics which is followed by a second first order
period with a much slower rate and a change in activation energy.
The time corresponding to the kinetic change was designated tc (Ta-
ble 3). The calculated rate constants and half lives for the periods
above and below the break were compared.
For time before tc, the oxidation rate corresponded to rapid deg-
radation of both surface carotene and internal carotene in contact
with the oxygen in pores or entrapped air bubbles. There was no
significant difference in the half-life of b-carotene (Table 3) between
the drying methods in this period as should be expected. However,
because of the different amounts of surface carotene, tc, correspond-
ed to a loss of b-carotene of 38±2%, 52±2% and 68±2%, respective-
ly for drum-dried, freeze-dried and spray-dried powder (Fig. 2). The
amount of carotene which was easily oxidized was process-depen-
dent, and tc was process-dependent (Table 2). For drum-dried pow- c
der, the slightly lower amount of surface carotene and the nonporous
structure reduced the duration of this fast oxidation period.
At times greater than tc, the matrix density and distance to the
entrapped material would limit oxygen transfer so a slower rate was
found. The equivalent half-life of the drum-dried b-carotene was
nearly 2 yr (Table 2). Also at times greater than tc, the kinetic half-
life of the spray-dried carotene was 189 days at 25°C, similar to the
value of 209 days at 21°C reported by Wagner and Warthesen (1995)
. The better retention with drum-dried powder could be explained by
the larger particle size, but may be due to the state of the matrix.
Collapse of the maltodextrin 25 DE during drum-drying can lead to
a more dense matrix; however, the pyncnometer results (Table 2) did
not confirm this. Thus particle size seemed to be the major factor
affecting stability in the second period. Spray-dried and freeze-dried
powders oxidized faster in the second period because of the shorter
distance for oxygen diffusion through the wall. Since both had the
same solids density but the freeze-dried particles were double the
size, we expected the spray-dried product to oxidize faster. The higher
bulk density of the spray-dried product suggests only that the parti- Fig. 3–Variation of the colorimetry parameter “L” and “a” during
storage of b-carotene encapsulated in a maltodextrin 25 DE by
cles could fit more compactly and this had no effect on oxidation spray-drying (a), drum-drying (b), and freeze-drying (c). Stored at
rate. In comparing the amount of carotene left after drying, the spray- 25°C, 35°C and 45°C and both 11% RH and 32% RH.

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 Encapsulation for Carotene Preservation . . .
dried product exceeded 70% loss at 15 wk, with an additional 8 wk
to reach a total of 70% loss for the freeze-dried product and 41 wk
for the drum-dried product.
a of b-carotene reduced the intensity of the pink color of the powders
b moderately until a point at which the change increased faster. At the
c Bushway, R.J. and Wilson, A.M. 1982. Determination of a- and b-carotene in fruits
Fig. 4–Correlation between colorimetry parameters “L0-L” (•) and
“a0-a” ( ), and b-carotene retention in spray-dried (a), drum-dried
(b) and freeze-dried (c) maltodextrin 25 DE.
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Color changes during storage
Pure b-carotene has a dark red color while the maltodextrin 25
DE is white. When mixed and dried, the spray-dried, freeze-dried
and drum-dried powders had initial values of “L” (Lightness) of 66.7,
52.1, 59.5 and the values of “a” (Redness) were 17.8, 32.0, 21.2
respectively. These initial variations between e powders resulted es-
sentially from the capsules structures and the amounts of surface
carotene left.
During storage, “a” decreased as “L” increased since oxidation
increasingly revealing the white color of the maltodextrin (Fig. 3).
“L” and “a” were good indicators for b-carotene degradation and the
profile of the curves coincide with the retention ( Fig. 3). The degra-
dation of b-carotene as a function of temperature was more obvious
when the color parameters were measured. The drum-dried powder
showed well separated curves for each temperature. In addition, the
influence of the relative humidity on color changes during storage of
the drum-dried powder was more obvious (Fig. 3). Higher storage
relative humidity led to higher “L” and lower “a” with time. The
parameter “b” was not a good indicator of carotene retention be-
cause it characterizes yellowness to blueness and these colors were
not dominant.
Relationship between “L”, “a” and percentage
b-carotene retention
The relationship between changes in “L” and “a” with b-caro-
tene retention was observed (Fig. 4). At the start, “L0-L” increased
same time, “a0-a” did not change until this same point when it dropped
sharply. This point corresponded well to the time when the rapid
oxidation period of carotene ceased. The change also corresponded
with the estimated amount of surface carotene for each preparation.
Overall, based on chromametric and spectrophotometric measure-
ments, drum-drying gave the best retention of b-carotene during stor-
age due to the larger particle size with a given wall/ingredient ratio.
This process is generally not used industrially for encapsulation of
nutritional or flavor components but should be considered because
of the higher cost for spray- or freeze-drying. The short shelf life of
25 wk for a 50% loss indicated likely problems for the addition of b-
carotene to foods. Some companies have developed very elaborate
encapsulation procedures for b-carotene but the cost is very high.
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Ms received 2/3/97; revised 7/14/97; accepted 7/22/97.
We acknowledge the French “Ministere de l’Education Nationale, de l’Enseignement Superieur et
de la Recherche” and the “North Atlantic Treaty Organization” for support of Dr. De Sobry and
Fundagao de Amparo a’ Pesquisa do Estado de São Paulo-FAPESP for support of Dr. Netto. This
project was supported in part by the Univ. of Minnesota Agricultural Experiment Station and is
published as scientific paper series # 97118000.
12/3/97, 2:21 PM