Lebensm.-Wiss. u.-Technol.

, 32, 290}298 (1999)

Apple Juice Clari"cation Using Micro"ltration and

Ultra"ltration Polymeric Membranes
B. Girard* and L. R. Fukumoto

Agriculture and Agri-Food Canada, Paci"c Agri-Food Research Centre, 4200 Highway 97S,
Summerland, B.C., V0H 1ZO (Canada)
(Received July 7, 1998; accepted April 12, 1999)

The yux behavior of polyethersulfone (0.2 lm), polyvinylidene -uoride (0.2 lm), cellulose (0.2 lm, 100 kDa, 30 kDa, 10 kDa), and
polysulfone (0.2 lm, 100 kDa, 30 kDa, 10 kDa) membranes was examined during dead-end ,ltration of apple juice. Membranes with
molecular weight cut-o+ of 30 and 100 kDa had superior -ux performance to 0.2 lm or 10 kDa membranes. A cross-ow system
equipped with various tubular polymeric membranes was also used to clarify apple juice at a temperature of 503C, a crossyow velocity of
3.3 m/s and a transmembrane pressure of 414 kPa. Steady state yuxes increased as the molecular weight cut-ow increased from 9 to
200 kDa. When challenged with P. diminuta, log reduction values between 6 and 7 were obtained with the cross-ow tubular polymeric
system. Membranes between 20 and 200 kDa produced juices with similar initial characteristics that underwent comparable changes
during storage at 4, 25 and 353C over 4}16 wk. The impact of xltration through the 9 kDa membrane was however noticeable on the
physico-chemical properties since the apple juice had a green tint, lower soluble solids, lower yavanol content, and experienced minimal
changes in browning and turbidity.

Keywords: micro"ltration; ultra"ltration; polymeric membrane; apple juice; physicochemical properties; microbial challenge;
sensory evaluation

Introduction membranes. The 0.1 km membrane permeate was darker

The use of polymeric membranes is widespread for the
clari"cation of apple juice by ultra"ltration. Padilla and
McLellan (1) studied the "ltration of apple juice through
10, 50, 100 and 500 kDa polysulfone hollow "ber mem-
branes. Initial #ux increased with molecular weight cut-
o! (MWCO) but the "ltered juice from all membranes
had similar acidity, soluble solids and sensory quality.
Although phenolic content was lower with the 500 kDa,
it generally increased with MWCO as did total solids.
The juice from the 100 and 500 kDa membranes had
higher turbidity and brown color than the other mem-
branes. All juices became turbid and browned during
storage at 43 3C over 6 months but no signi"cant changes
were observed at 18 3C. Sheu et al. (2) used 20 and 50 kDa
polysulfone membranes in a plate and frame con"gura-
tion to "lter apple juice. The average #ux was 20 to 40
L/m h higher for the 50 than the 20 kDa membrane. Wu
et al. (3) compared 0.1 km ceramic, 50 kDa poly-
sulfone hollow "ber and 5 kDa polysulfone spiral-wound
PARC Contribution No. 1051
* To whom correspondence should be addressed.
0023-6438/99/050290#09 $30.00
All articles available online at http://www.idealibrary.com on
and had higher turbidity, total solids and soluble solids.
Rao et al. (4) found that apple juice permeate
from a 30 kDa polyamide membrane contained more
volatiles than permeate from a 50 kDa polysulfone mem-
brane.
Various membrane con"gurations of polymeric mem-
branes have been reported for ultra"ltration of apple
juice including hollow "ber (1, 3, 5), spiral-wound (3), and
plate and frame (2). Although these con"gurations have
better packing densities, they usually have narrow chan-
nels which make these designs more susceptible to mem-
brane fouling than tubular con"gurations. Porter (6) lists
various other advantages and disadvantages of the vari-
ous con"gurations. Since freshly pressed apple juice
contains a considerable amount of particulate matter,
pre"ltration is often necessary when using designs with
narrow channels. RoK sch (7) found apple juice could be
concentrated approximately 70 times using a 25 mm
diameter tubular system.
Few studies have examined the e!ect of membrane ma-
terial on ultra"ltration of apple juice. This paper focused
on the application of polymeric membranes for apple
juice "ltration and paralleled additional work on ceramic
membrane published elsewhere (8). Initially, a stirred cell
Article No. fstl.1999.0554

290

system was used for an examination of the e!ect of
membrane material on apple juice "ltration. Apple juice
was also "ltered through a pilot plant tubular system
using ultra"ltration polymeric membranes. The e!ects of
cross#ow velocity and transmembrane pressure on #ux
were determined on the tubular system to optimize these
operating parameters. A microbial challenge was carried
out to establish the e!ectiveness of selected tubular
polymeric ultra"ltration membranes in removing micro-
organisms. Batches of juice were also "ltered through
di!erent membranes to determine the e!ect of MWCO
on #ux behavior and on juice properties. Filtered juices
were membrane sterilized, aseptically packaged and then
stored at 4, 25 and 35 3C for up to 16 wk to examine their
storage stability.
Materials and Methods
Apple juice
A blend of McIntosh, Spartan and Red Delicious apples
(Malus domestica Borkh.) was obtained from the Sum-
merland Research Centre orchards and from other or-
chards in the British Columbia Okanagan Valley. The
apples were stored at 0 to 2 3C for several weeks until
processed. Apples tested negative for starch using the
method of Lau (9).
Apples were brought to room temperature before pro-
cessing. They were manually washed and then hammer-
milled through a 1.3 cm aperture screen. The mash was
held for 60 min at room temperature to promote oxida-
tion prior to juice extraction with a screw press (Vetter
Model BA6006 Type 1/2, Postfach, Germany). Pectinex
Ultra SP (0.012 mL/100 mL) and Pectinex 100L
(0.006 mL/100 mL) enzymes (Novo Nordisk Biochem
North America Inc., Franklinton, NC, U.S.A.) was added
and the juice was kept overnight at 4 3C in a stainless
steel tank after #ushing the headspace with N . Before

"ltration, complete depectinization was ensured by in-
creasing the temperature of the juice to 50 3C for 2 h
using a tube-in-shell heat exchanger.
The depectinization procedure was monitored using
an alcohol test and a centrifugation test. The alcohol
test consisted of mixing equal volumes of juice with
ethanol (95 g/100 mL) in a test tube. The presence of
a precipitate indicated that pectin was still present. The
centrifugation test was modi"ed from the method of Ishii
and Yokotsuka (10) and consisted of centrifuging 40 mL
of juice at 2500;g for 5 min at 10 3C. The supernatant
was "ltered through Whatman No. 41 "lter paper and
the turbidity measured using a Hach Ratio/XR tur-
bidimeter (Model 43900, Hach Co., Loveland, CO,
U.S.A.). All batches of juices were depectinized to the
same extent.
Stirred cell system
Depectinized apple juice was "ltered through a Model 52
stirred cell of 43 mm diameter (Amicon Canada Ltd.,
Oakville, ON, Canada). Polyethersulfone (PES, Supor
200-60301) and polysulfone (PS, HT Tu!ryn 200-66199)
291
lwt/vol. 32 (1999) No. 5
disc membranes (47 mm diam.) of 0.2 km pore size were
obtained from Gelman Sciences Inc. (Montreal, PQ,
Canada). Mixed cellulose esters (CE, MF type, GSWP-
04700) and hydrophilic polyvinylidene #uoride (PVDF,
Durapore, GVWP-04700) disc membranes (47 mm
diam.) of 0.2 km pore size were supplied by Millipore
Corp. (Mississauga, ON, Canada). PS type membrane
discs (43 mm diam.) of 10 kDa (PM10-13122) and
30 kDa (PM30-13222), and cellulosic type membrane
discs (43 mm diam.) of 10 kDa (YM10, 13622), 30 kDa
(YM30, 13722) and 100 kDa (YM100, 14422) were pro-
vided by Amicon Canada Ltd. (Oakville, ON, Canada).
PS membrane discs of 100 kDa (GR40PP) were cut from
DDS (De Danske Sukkerfabrikker) Lab 20 model mem-
branes (Dow Danmark A/S, Separation Systems,
Nakskov, Denmark). Membrane discs that were not de-
signed for the Amicon system were carefully cut and
"tted for use.
Juice (50 mL) was "ltered through the stirred cell at
room temperature with 276 kPa N pressure and a stirrer

rotation of 750 rpm. The headspace in the stirred cell
was #ushed with N before "ltration. The weight

of permeate obtained from the cell was monitored over
time to calculate #ux. The membrane and fouling layer
resistances were determined using the following equa-
tion:
*P
J" Eqn [1]
k(R #R )
K D
where J is the average #ux (kg/ms) observed be-
tween concentration factors of 7.5 and 11, *P is the
transmembrane pressure (Pa), k is the permeate viscosity
(Pa ) s), R is the membrane resistance (m/kg), and R is
K D
the fouling layer resistance (m/kg). Water and juice
#ux for the CE and PS micro"ltration membranes
(0.2 km) were repeated six times for evaluating coe$-
cients of variation. All other measurements were done in
duplicates.
Tubular polymeric membrane xltration system
A B1 twin-entry tubular membrane module (PCI Mem-
brane Systems Ltd., Eden Prairie, MN, U.S.A.) consisting
of two parallel sets of nine tubes in series was connected
to a membrane "ltration unit (APV Membrane Systems,
Tonawanda, NY, U.S.A.). The tubes had a diameter of
12.5 mm and the total surface area for all 18 tubes was
0.9 m. Several PCI membranes of di!erent MWCOs
and composition were tested including 200 kDa PVDF
(FP200), 100 kDa PVDF (FP100), 25 kDa PES (ES625),
20 kDa PS (PU120) and 9 kDa PES (ES209). Due to the
limited commercial availability, membranes made with
di!erent material but the same MWCO could not be
compared. The "ltration unit was setup to run in a batch
mode for a feed and bleed circuit. The feed temperature
was regulated by a heat exchanger connected to the feed
tank. Both feed and recirculation pumps had variable
drives.
For #ux studies, depectinized juice (50 L) was recir-
culated through either 25 kDa PES or 200 kDa PVDF
lwt/vol. 32 (1999) No. 5
membranes. Only two tubes in parallel were used corres-
ponding to a membrane area of 0.1 m. Both the per-
meate and retentate (bleed) were returned to the feed
tank which was continuously #ushed with N . The feed

pump was set to deliver 6 L/min and the recirculation
pump was increased over 15 min to the desired cross#ow
velocity (CFV). Cross#ow velocities of 3.3 and 6.7 m/s
corresponded to recirculation rates of 49 and 98 L/min
and pressure di!erentials of 83 and 276 kPa, respectively.
The recycle #ux was continuously monitored using
a graduated cylinder and stopwatch. The system was
allowed to equilibrate for 30 to 50 min before increasing
the transmembrane pressure (TMP) by adjusting the
retentate outlet valve.
Prior to batch concentration runs and microbial
challenge tests, the membranes were sanitized by circula-
ting a 50 mg/L chlorine solution at 50 3C for 30 min
then rinsing with distilled water. The permeate tank
and lines underwent a sterilization treatment at 121 3C
and 104 kPa for 15 min. Sterile N was used to

maintain a positive pressure in the system after
cooling.
Batches of apple juice (200 to 240 L) were "ltered through
the above mentioned membranes. The operating condi-
tions for these batch concentration runs were 3.3 m/s
CFV, 414 kPa TMP, and 50 3C. The feed pump provided
a #owrate of 6 L/min and the feed tank was continuously
#ushed with N . The #ux was monitored using an elec-

tromagnetic #owmeter (Model M053724010R100A, ABB
Kent-Taylor, Rochester, NY, U.S.A.) as the permeate was
separately collected in a SS tank. The juice was processed
to a concentration of three times for the 9 kDa mem-
brane and 10 times for the other membranes. Prior to
juice "ltration, the water #ux was measured under the
same conditions. The membrane and fouling layer resist-
ances were calculated using Eqn [1]. The "ltration unit
was cleaned-in-place using a solution of 0.1 to 0.15
g/100 mL Ultrasil 10 (Klenzade, Mississauga, ON,
Canada) with 100 to 200 mg/L free chlorine. Following
a rinse with water, the cleaning cycle was repeated a sec-
ond time.
Bottling and storage
Immediately before bottling, the clari"ed juice was
"ltered through a sterile 0.45 km Supor DCF capsule
(Gelman Sciences Inc., Montreal, PQ, Canada). The
capsule had a 0.8 km pre"lter and a 0.45 km hydrophillic
PS "lter. This "ltration step ensured that microbial
growth would not occur during storage. The juice was
bottled into 250 mL glass jars with twist cap lids in
a laminar #owhood. The jars and lids were steam steriliz-
ed prior to use. The headspace of the jars was #ushed
with N "ltered through a 0.2 km PTFE membrane Hi-

Flo Sol-Vent capule (Gelman Sciences). Juices were
stored at 35, 25 and 4 3C in the dark. At 35 3C, samples
were removed after 1, 2, 3 and 4 wk storage. At 25 and
4 3C, samples were removed after 4, 8, 12 and 16 wk
storage. Initial and stored samples were frozen at
!30 3C until analysed.
292
Microbial challenge test
The microbial retention of the 9 kDa and 25 kDa PES
membranes was tested with Pseudomonas diminuta
(Brevundimonas diminuta) ATCC 19146 (American
Type Culture Collection, Rockville, MD, U.S.A.). The
culture was propagated in nutrient broth at 30 3C for
24 h. The cells were separated by centrifugation at
5 000;g for 15 min at 4 3C and were resuspended in 50 L
of 0.1 g/100 mL peptone to challenge a membrane with
1;10 cfu/cm. The bacterial test solution was circulated
through the membrane at 25 3C, 2 m/s CFV and 207 kPa
TMP with the feed pump delivering 6 L/min. The solu-
tion was recycled for 60 min before withdrawing per-
meate and retentate samples. CFV and TMP were then
increased to 3.3 m/s and 414 kPa, respectively, and sam-
ples were taken again after 60 min.
Aliquots of retentate were serially diluted with
0.1 g/100mL peptone and spread plated in duplicate on
nutrient agar. Plates were incubated at 25 3C for 72 h.
Two 1000 mL samples of permeate were membrane "l-
tered through sterile 0.45 km membranes. The mem-
branes were incubated on absorbent pads soaked with
nutrient broth at 25 3C for 72 h.
Analytical measurements
Samples were analysed for color, turbidity, viscosity,
soluble solids, titratable acidity, #avanols and protein.
Brown color was measured at an absorbance of 420 nm
using a Beckman DU 640 spectrophotometer (Beckman
Instruments, Inc., Fullerton, CA, U.S.A.). Color was also
assessed spectrophotometrically with a CIE L*, a* and
b* Color Determination and Matching program Version
1.0 (Beckman Instruments, Inc.). Values were calculated
for standard illuminant C and the CIE 1964 Supple-
mentary Standard Observer. Turbidity was determined
with a Hach Ratio/XR turbidimeter (Model 43900, Hach
Co., Loveland, CO, U.S.A.). A Brook"eld LVDV-II#
viscometer with a UL adapter (Brook"eld Engineering
Laboratories, Inc., Stoughton, MA, U.S.A.) was used to
measure viscosity at a shear rate of 73 s\. Soluble solids
were assessed with a Reichert Abbe Mark II digital
refractometer (AO Scienti"c Instruments, Bu!alo, NY,
U.S.A.). Juice samples (10 g) were titrated with 0.1
N NaOH to an endpoint of pH 8.1 using a Metrohm 686
Titroprocessor and 665 Dosimat (Metrohm Ltd. Switzer-
land) and titratable acidity was expressed as g malic acid
per 100 mL juice. Flavanol content was determined by
the acidi"ed vanillin method of Broadhurst and Jones
(11) using (-)-epicatechin (Sigma Chemical Co., St. Louis,
MO, U.S.A.) as standard. Initial protein content was
measured using the Kjeldahl method. Juice samples (5 g)
were dried at 70 3C in a vacuum oven (104 kPa) prior to
digestion. Nitrogen was measured with a Technicon
AutoAnalyzer II (Technicon Industrial Systems,
Tarrytown, NY, U.S.A.) using a colorimetric assay based
on the reaction of ammonia, sodium salicylate, sodium
nitroprusside and sodium hypochlorite in a bu!ered al-
kaline medium which produced an ammonia-salicylate
complex with an absorbance maximum at 660 nm. A fac-
tor of 6.25 was used to convert nitrogen concentration to
 lwt/vol. 32 (1999) No. 5

protein concentration. For all analyses, measurements

were made on two replicate samples.

Sensory Analysis
Di!erences between juices "ltered through the various
membranes were compared using triangle tests. Eighteen
judges were selected from sta! at the Paci"c Agri-Food
Research Centre. Juices were stored at !30 3C after
initial processing. Prior to sensory evaluation, the juices
were thawed at 4 3C. Juice samples (30 mL) were pre-
sented to each judge in covered black wine glasses with
random three-digit codes. The juices were allowed to
equilibrate at room temperature for 30 min before pre-
sentation. Judges were asked to smell and then taste a set
of three glasses in the order given before selecting the
odd sample. The triangle tests were completely random-
ized for the odd sample and the order of presentation.
The level of signi"cance was determined according to
Larmond (12).

Results and Discussion

Stirred cell
Micro"ltration (MF) membranes of 0.2 km pore size had
similar steady state #ux for apple juice "ltered through
the stirred cell. Based on water and juice #ux from cellu-
lose (25267$2648 L/mh and 67.0$6.6 L/mh, respec-
tively) and polysulfone (2588$243 L/mh and 64.3$
7.2 L/mh, respectively) MF membranes, coe$cients of
variation varied between 9.4 and 11.1%. Delineation
between membranes were more apparent based on their
relative #ux (permeate #ux/pure water #ux) (Fig. 1A).
PVDF and PS comparatively gave higher values than
PES. These di!erences were consistent with the results of
Riedl et al. (13) and have been associated with membrane
surface morphology rather than membrane surface hy-
drophobicity. Smooth membranes (e.g. PS and nylon)
produced a dense surface layer whereas this same layer
on rougher membranes (PES and PVDF) was more
open (13).
As with MF membranes, the initial relative #ux of
100 kDa membranes were high and the rates of per-
meate production decreased rapidly (Fig. 1B). Ultra"ltra-
tion (UF) membranes of 30 kDa had initial #ux declines
intermediate to 100 and 10 kDa. Relative #ux of all UF
membranes were also higher than that of MF membranes
by at least "ve to ten fold (Fig. 1A and B). Once
the membrane resistances were taken into account, less
fouling was experienced by UF membranes of 30 and
100 kDa as evidenced by lower fouling layer resistances
(Table 1). These results indicated that an optimum
apple juice "ltration #ux exists between 0.2 km
and 10 kDa membranes. Flux was expected to be lower
for the 10 kDa due to high membrane resistance. Apple
juice particulates of less than 0.2 km likely caused
pore plugging and fouling in the MF membrane lead-
ing to increased #ux reduction compared to UF mem-
branes.
Fig. 1 Relative #ux of depectinized apple juice in a stirred cell
(TMP, 276 kPa; stirrer rotation, 750 rpm; temperature, 233C)
through micro"ltration (A) membranes (}䉬}) 0.2 km cellulose;
(}䉱}) 0.2 km polyvinylidene #uoride; (*;*) 0.2 km polysulfone;
(}䊏}) 0.2 km polyethersulfone; and ultra"ltration, (B) mem-
branes (}䉬}) 100 kDa cellulose; (}䉱}) 30 kDa cellulose; (*;*)
10 kDa cellulose; (}䊏}) 100 kDa polysulfone; (}䊉}) 30 kDa
polysulfone; (}"}) 10 kDa polysulfone.
Flux studies with tubular membranes
Typical behavior for cross#ow UF membranes is
generally noted by an initial #ux increase followed by
a plateau as TMP is ramped from low to high values. The
pressure independent region of #ux is due to concentra-
tion polarization and the formation of a gel layer (14).
Using the cross#ow tubular membrane system, the high-
er CFV (6.7 m/s) led to a large increase in recycle #ux
with the 200 kDa PVDF membrane, but this #ux
improvement was not observed with the 25 kDa PES
membrane (results not shown). In cross#ow membrane
"ltration processes, CFV is known to improve #ux due to
higher shear rates promoting the removal of components
deposited on the membrane surface (14). At higher
MWCO (200 kDa), increasing CFV up to 414 kPa im-
proved #ux because the fouling layer was a limiting
factor. At lower MWCO (25 kDa), the pore size rather
than the fouling layer was more restrictive and increased
turbulence at the membrane surface was therefore not as
e!ective.

293
lwt/vol. 32 (1999) No. 5

Table 1 Membrane resistance (R ), fouling layer resistance (R ) and total resistance (R ) for apple juice "ltration
K D 2
with a stirred cell system.

Membrane Resistance?@

R R R
K D 2
(;10 m/kg) (;10 m/kg) (;10 m/kg)

0.2 km cellulose (Millipore) 3.9 1054.7 1058.6

0.2 km polyethersulfone (Gelman) 17.5 1233.7 1251.2
0.2 km polysulfone (Gelman) 38.4 1064.1 1102.4
0.2 km hydrophilic polyvinylidene #uoride (Millipore) 38.8 1088.6 1127.4
100 kDa polysulfone (DDS) 189.1 624.4 813.5
30 kDa polysulfone (Amicon) 143.5 760.9 904.4
10 kDa polysulfone (Amicon) 492.0 1050.4 1542.4
100 kDa cellulose (Amicon) 86.1 747.2 833.3
30 kDa cellulose (Amicon) 216.2 701.7 917.9
10 kDa cellulose Amicon) 1118.3 345.2 1463.5

? Transmembrane pressure, 276 kPa; stirrer speed, 750 rpm; temperature, 23 3C

@ Values for 0.2 km cellulose and polysulfone membranes are averages of six replicates while the remaining values are averages of
two replicate samples

Table 2 Challenge tests of tubular polyethersulfone tion of microorganisms in "nished product compared to
membranes with Pseudomonas diminuta levels that may be present in untreated juice. A tangential
#ow system using mineral membranes has been reported
Sampling time and conditions? Microbial counts@ for the production of cold sterile apple juice (15). The use
of a "nal dead-end "lter prior to bottling could however
Retentate Permeate ensure microbial stability for both polymeric and ce-
(cfu/L) (cfu/L) ramic membranes.
9 kDa membrane
Initial 14.0;10 *
After 1 h at 25 3C, 2 m/s Batch concentration with tubular membranes
CFV and 207 kPa TMP 13.3;10 1.2;10 A batch concentration study entails the monitoring of
After 1 h at 25 3C, 3.3 m/s #ux as the retentate returns to the feed tank and the
CFV and 414 kPa TMP 11.0;10 3.3;10
permeate is removed. The stabilized #ux increased with
25 kDa membrane membrane MWCO notwithstanding the di!erences in
Initial 12.1;10 *
After 1 h at 25 3C, 2 m/s
membrane material and manufacture (Fig. 2). The high-
CFV and 207 kPa TMP 11.6;10 3.5;10 est steady state #ux (236 L/mh) was obtained with the
After 1 h at 25 3C, 3.3 m/s 200 kDa PVDF membrane and the 9 kDa PES mem-
CFV and 414 kPa TMP 7.9;10 1.2;10 brane had the lowest #ux (14 L/mh). Relative #ux for the
UF membranes under cross#ow conditions were in the
? CFV, cross#ow velocity; TMP, transmembrane pressure
@ Results are the averages of two replicate samples
same range as those obtained with the stirred cell system.
Although PVDF membranes were of larger pore size
(100 kDa and 200 kDa), their #ux resistances due to the
Microbial challenge test fouling layer (R ) were smaller than the 20 kDa PS and
D
During the challenge tests of the 9 and 25 kDa PES 9 kDa PES (Table 3). Comparison of absolute #ux values
membranes, the concentrations of P. diminuta in the with other studies is often di$cult because of di!erences
retentate decreased slightly with time as cells adhered to in operating conditions, depectinization treatment and
the membrane and piping surfaces (Table 2). The low membrane type. The trends were consistent with that of
number of colony forming units (cfu) detected in the Padilla and McLellan (1), although #ux results
permeates indicated that the membranes "ltered out were lower for all membranes, except the 200 kDa mem-
most microorganisms. As P. diminuta is one of the brane.
smallest known bacteria (around 0.2 km), the 9 and Turbidity, viscosity, titratable acidity, and nitrogen (pro-
25 kDa membranes were e!ective in removing microor- tein) content were similar in all juices (Table 4). The
ganisms to log reduction values between 6 and 7. As the yellow/brown color of the juices decreased with mem-
CFV and TMP were increased, more microorganisms branes of smaller MWCOs. The visual appearance of the
passed through the membrane system. With a UF ce- juice "ltered through the 9 kDa membrane was distinctly
ramic membrane module, a log reduction value greater di!erent in that a slight green tint was evident. This
than 9 can be obtained (8). The tubular polymeric mem- membrane also retained more sugars and #avanols than
brane system used in this study can nevertheless meet the the other membranes as noted by reduced soluble solids
present FDA proposal of achieving a 100 000 fold reduc- and #avanol content. Along with the #avanols, the 9 kDa

294
 lwt/vol. 32 (1999) No. 5

Table 5 Triangle test comparisons of apple juice "ltered

through various ultra"ltration membranes

Comparison Correct Level of

responses? signi"cance

200 vs. 100 kDa 9 NS@

200 vs. 20 kDa 13 P(0.001
200 vs. 9 kDa 14 P(0.001
100 vs. 20 kDa 7 NS
100 vs. 9 kDa 14 P(0.001
20 vs. 9 kDa 15 P(0.001

? a panel of 18 judges was used

@ n.s."not signi"cant

membrane retained phenolic compounds responsible for

Fig. 2 Permeate #ux and relative #ux of depectinized apple
juice through ultra"ltration tubular membranes (TMP,
414 kPa; CFV, 3.3 m/s; temperature, 50 3C). (}䉬}) 200 kDa
polyvinylidene #uoride; (;) 100 kDa polyvinylidene #uoride;
(}䉱}) 20 kDa polysulfone; (}䊏}) 9 kDa polyethersulfone
the decrease in yellow color (A , b*). The green tinge
 
possibly associated with the presence of chlorophyll
likely became apparent once the masking e!ect of the
yellow pigment was partially removed.
Triangle tests were carried out to compare #avor charac-
teristics of the juices "ltered through various membranes
(Table 5). Although the juices from the 200 and 20 kDa
membranes were signi"cantly di!erent from each other,
their respective di!erences with the 100 kDa membrane
were too small to be detected. All other tested membrane

Table 3 Membrane resistance (R ), fouling layer resistance (R ) and total resistance (R ) for apple juice "ltration
K D 2
with a cross#ow tubular system

Membrane Resistance?@

R R R
K D 2
(;10 m/kg) (;10 m/kg) (;10 m/kg)

200 kDa polyvinylidene #uoride 128.5 322.6 451.1

100 kDa polyvinylidene #uoride 164.3 772.3 936.6
20 kDa polysulfone 442.3 1817.4 2259.7
9 kDa polyethersulfone 699.7 6670.4 7370.1

? Transmembrane pressure, 414 kPa; cross#ow velocity, 3.3 m/s; temperature, 50 3C

@ Results are averages of two replicate samples

Table 4 Properties of apple juice "ltered through di!erent tubular polymeric membranes

Property? Tubular polymeric membrane@

200 kDa PVDF 100 kDa PVDF 20 kDa PS 9 kDa PES

A 0.44 0.38 0.34 0.18

 
L* 95.9 96.2 96.6 99.0
a* !5.4 !4.9 !4.3 !4.8
b* 30.6 27.7 24.8 14.3
Turbidity (NTU) 0.12 0.09 0.16 0.15
Viscosity at 253C (cps) 1.38 1.37 1.38 1.36
Soluble solids (3Brix) 12.7 12.3 12.2 11.4
Titratable acidity 0.44 0.37 0.34 0.39
(g malic acid/100 mL juice)
Flavanol content (mg/L) 66 80 108 17
Protein content (mg/L) 29 29 23 34

? Results are the averages of two replicate samples

@ PVDF, polyvinylidene #uoride; PS, polysulfone; PES, polyethersulfone

295
lwt/vol. 32 (1999) No. 5
Fig. 3 E!ect of storage temperature and time on turbidity of apple juice "ltered through (a) 200 kDa PVDF, (b) 100 kDa PVDF,
(c) 20 kDa PS, and (d) 9 kDa PES membranes. (}䉬}) 35 3C; (}䊏}) 25 3C; (}䊉}) 4 3C
combinations were also found to be signi"cantly di!er-
ent. Judges noticed the largest di!erences between juices
"ltered through the 9 kDa membrane and the other
membranes. They commented that the 9 kDa membrane
juice was thin (low body/mouthfeel/viscosity), had less
#avor and had an o!-#avor (medicinal/metallic). Besides
retaining sugars and #avanols, the 9 kDa membrane may
also have retained other #avor components.
Storage study
The viscosity, soluble solids and titratable acidity of the
juices did not change with either storage temperature or
time. In addition, no microbial growth was observed
during storage of the cold pasteurized juices. However,
turbidity increased over time with higher storage temper-
atures and membranes of larger MWCOs (Fig. 3). Cha-
nges were more pronounced at 35 3C as the rates of
chemical reactions generally increase with temperature.
The 200 kDa membrane had the most turbidity develop-
ment whereas the 9 kDa membrane had the least turbid-
ity formation. Turbidity has previously been reported to
increase with storage of juice (1).
Haze formation in UF clari"ed apple juice is a poten-
tial problem. Polymerization of phenolics and interac-
tions with other components (e.g. proteins) can lead
to turbidity in fruit juice products (16, 17). Evidence
that phenolics could be involved in turbidity develop-
ment is supported by the #avanol content changes ob-
served during storage (Fig. 4). Flavanol content in all
membrane "ltered juices decreased in a similar fashion
with storage temperature and time. On a comparative
basis, #avanol content values among juices were an indi-
cator of the degree of #avanol polymerization (18). Dur-
296
ing storage, changes in #avanols paralleled increases in
turbidity and yellow/brown color. The 9 kDa membrane
initially retained more #avanols than the other mem-
branes and the juice consequently had the lowest changes
in turbidity.
The juices from all membranes had similar color cha-
nges as measured using the absorbance at 420 nm
(Fig. 5). A pattern characterized by an initial decrease
of about 0.1 absorbance unit followed by an increase
of more than 0.1 unit was observed for most juices
stored at 25 and 35 3C. The rates at which the changes
occured were three times faster at 35 3C than at 25 3C.
The oxidation and/or polymerization reactions involving
the phenolic compounds may have created intermediate
molecular species which absorbed less at 420 nm for
a period of time. The length of this period was dependent
on temperature. All juices stored at 4 3C consistently
decreased in yellowness but did not increase again during
the 15 wk period. The degradation products which pro-
gressively regained the partial loss of absorbance at
420 nm were not generated at 4 3C probably due to
a slower reaction rate.
Conclusions
Initial testing of di!erent membrane types during dead-
end "ltration of apple juice indicated that PVDF and PS
membranes gave higher relative #ux than PES and CE
membranes. In addition, 0.2 km or 10 kDa membranes
had higher fouling layer resistances than 30 and 100 kDa
membranes. With tubular polymeric UF membranes, the
#ux for depectinized apple juice improved as the
membrane MWCO increased from 9 to 200 kDa. Juices
 lwt/vol. 32 (1999) No. 5

Fig. 4 E!ect of storage temperature and time on #avanol content of apple juice "ltered through (a) 200 kDa PVDF, (b) 100 kDa
PVDF, (c) 20 kDa PS, and (d) 9 kDa PES membranes. (}䉬}) 35 3C; (}䊏}) 25 3C; (}䊉}) 4 3C

Fig. 5. E!ect of storage temperature and time on browning (A ) of apple juice "ltered through (a) 200 kDa PVDF, (b)
 
100 kDa PVDF, (c) 20 kDa PS, and (d) 9 kDa PES membranes. (}䉬}) 35 3C; (}䊏}) 25 3C; (}䊉}) 4 3C

"ltered through 200, 100 and 20 kDa membranes had
similar properties, but juice "ltered through a 9 kDa
membrane had lower soluble solids, #avanols and yel-
low/brown pigments. During storage at 4, 25 and 35 3C,
the viscosity, soluble solids and titratable acidity did not
change for all juices. Under these conditions, the cold
pasteurized juices were microbiologically stable. How-
ever, turbidity increased with storage especially for the
higher MWCO membranes. A slight decrease in #avanol
content and a slight increase in browning were also

297
lwt/vol. 32 (1999) No. 5
observed over time. Storage at refrigerated temperature
(4 3C) minimized these changes. Although the juice from
the 9 kDa membrane was physicochemically more stable
during storage, #ux performance was comparatively low
and the sensory characteristics were a!ected due to in-
creased membrane retention of sugar, phenolic and other
#avor components.
Acknowledgements
This study was done in collaboration with Sun-Rype
Products Limited of Kelowna, B.C. with the assistance of
the Industrial Research Assistance Program. The authors
would like to thank Dr M. Cli!, Dr P. Delaquis and
Mr T. Kopp for their assistance.
Written on behalf of the Department of Agriculture and
Agri-Food, Government of Canada.  Minister of Pub-
lic Works and Government Services Canada 1999
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