Environ. Sci. Technol.
2006, 40, 364-369
Power Densities Using Different
Cathode Catalysts (Pt and CoTMPP)
and Polymer Binders (Nafion and
PTFE) in Single Chamber Microbial
Fuel Cells
SHAOAN CHENG, HONG LIU, AND
B R U C E E . L O G A N * ,,
Department of Civil and Environmental Engineering and The
Penn State Hydrogen Energy (H2E) Center, The Pennsylvania
State University, University Park, Pennsylvania 16802
Cathode catalysts and binders were examined for their
effect on power densities in single chamber, air-cathode,
microbial fuel cells (MFCs). Chronopotentiometry tests
indicated that the cathode potential was only slightly reduced
(20-40 mV) when Pt loadings were decreased from 2 to
0.1 mg cm-2, and that Nafion performed better as a Pt binder
than poly(tetrafluoroethylene) (PTFE). Replacing the precious-
metal Pt catalyst (0.5 mg cm-2; Nafion binder) with a
cobalt material (cobalt tetramethylphenylporphyrin, CoTMPP)
produced slightly improved cathode performance above
0.6 mA cm-2, but reduced performance (<40 mV) at lower
current densities. MFC fed batch tests conducted for 35
cycles (31 days) using glucose showed that replacement of
the Nafion binder used for the cathode catalyst (0.5 mg
of Pt cm-2) with PTFE reduced the maximum power densities
(from 400 ( 10 to 480 ( 20 mW m-2 to 331 ( 3 to 360
( 10 mW m-2). When the Pt loading on cathode was reduced
to 0.1 mg cm-2, the maximum power density of MFC
was reduced on average by 19% (379 ( 5 to 301 ( 15
mW m-2; Nafion binder). Power densities with CoTMPP were
only 12% (369 ( 8 mW m-2) lower over 25 cycles than
those obtained with Pt (0.5 mg cm-2; Nafion binder). Power
densities obtained using with catalysts on the cathodes
were 4 times more than those obtained using a plain carbon
electrode. These results demonstrate that cathodes used
in MFCs can contain very little Pt, and that the Pt can even
be replaced with a non-precious metal catalyst such as
a CoTMPP with only slightly reduced performance.
Introduction
A microbial fuel cell (MFC) is a device that uses bacteria to
catalyze the conversion of organic matter into electricity (1-
9). Substrate is oxidized by bacteria generating electrons and
protons at the anode. Electrons are transferred through an
external circuit while the protons diffuse through the solution
to the cathode, where electrons combine with protons and
oxygen to form water. It is now known that no exogenous
mediators need to be added into an MFC (10, 11). It has been
found that several microorganisms including Shewanella
* Corresponding author phone: (814) 863-7908; fax: (814) 863-
7304; e-mail: blogan@psu.edu.
Department of Civil and Environmental Engineering.
The Penn State Hydrogen Energy (H2E) Center.
364 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 40, NO. 1, 2006
putrefaciens (4, 12, 13), Geobacteraceae (5, 14-17) Clostrid-
ium butyricum (18), and Rhodoferax ferrireducens (19) can
produce electricity in the absence of exogenous mediators
from chemicals such as glucose, acetate, lactate, pyruvate,
and formate. Mixed cultures of bacteria have been also
reported to generate electricity from domestic wastewater
(6-8, 20) and marine sediments (4, 15).
The performance of an MFC is influenced by several
factors including the microbial activity, chemical substrate
(fuel), type of proton exchange material (or even absence of
this material), resistance of the circuit, and anode and cathode
materials (4-6, 8, 9, 19, 21-23). The cathode performance
is an important factor to the performance of an MFC due to
the poor kinetics of oxygen reduction in the medium (6, 24).
Cathode performance can be improved if Pt catalysts can be
made more effective at room temperature, if the internal
resistance of the reactor is reduced, or if more effective
oxidants than oxygen (such as ferricyanide) are used. For
example, power densities of MFCs have been increased by
replacing aqueous cathodes with either direct-air carbon
cathodes containing Pt (8, 24) or graphite electrodes con-
taining Fe3+ (22). Oh et al. (9) found that the maximum power
achieved using ferricyanide ion as oxidant in the cathode
chamber was 50-80% greater than that obtained with
dissolved oxygen and Pt. Power densities as large as 6000
mW m-2 have been reported for MFCs using ferricyanide
(23). However, ferrocyanide must be replaced after it is
reduced, while systems using oxygen can be continuously
operated and therefore self-sustaining.
MFCs produce lower power densities than other types of
fuel cells, but their most promising application in the near
future is likely to be as a process for wastewater treatment
(7, 25). Reducing the cost of the materials used to make MFCs
is essential for building an economical treatment system.
The typical manufactured components of an MFC are a
proton exchange membrane (PEM), Pt catalyst on the
cathode, and carbon electrodes. However, recent studies have
shown that the proton exchange membrane is not needed
for the operation of MFCs (8, 14) and that removing it actually
increases maximum power densities (8). Pt is an effective
catalyst used for both electrodes in hydrogen fuel cells, but
it is an expensive component of the MFC cathode. While
alternatives to Pt have been sought, none have approached
the performance of Pt in hydrogen fuel cells (26). Pt is used
on the cathode in air-cathode MFCs, so minimizing or
eliminating the need for Pt can reduce the system capital
costs. In most MFC studies commercially produced cathode
electrodes are used that contain 0.5 mg cm-2 Pt loading (8),
although graphite electrodes containing 0.28 mg/cm2 Pt have
also been used (24).
The effect of different Pt loadings has not been previously
examined for MFCs, and few alternatives to Pt have been
explored for use in air-cathode MFCs. The effect of Pt loading
on power generation has been examined for other types of
fuel cells, but these systems operate under much different
conditions of pH (highly acid or alkaline conditions; refs
27-29) and temperature (50-1000 C), and therefore the
results are not directly translatable to the performance of
MFCs. Maximum power densities in aqueous cathode MFCs
can be reduced by an order of magnitude when Pt is not
used on the cathode (30). When Pt is used as a catalyst on
a carbon electrode, it is usually bound to the electrode
substrate using a polymer. Perfluorosulfonic acid (Nafion)
and poly(tetrafluoroethylene) (PTFE) are two commonly used
binders for Pt in chemical fuel cells (31-33), but Nafion can
cost 500 times more than PTFE (mass basis). Nafion is a
10.1021/es0512071 CCC: $33.50 2006 American Chemical Society
Published on Web 11/23/2005
proton conductive polymer that has hydrophilic ionic
clusters, a hydrophobic base, and a transition region that
allows for effective proton transfer to the catalyst. PTFE is
a highly hydrophobic material that is useful in limiting water
leakage through the cathode in an MFC and it is well-known
to have good oxygen transfer properties, but unlike Nafion
it is not an electrolyte. In addition, because PTFE is highly
hydrophobic, it can cause the environment of the catalyst to
become too dry, limiting effective proton transfer to the
catalyst. The effect of different binders on the performance
of air-cathode MFCs has not been previously addressed.
In this study, we examined the effect of Pt loading (0.1-2
mg cm-2) using two different binders on the electrochemical
performance of the cathodes in a bacteria-free electrochemi-
cal cell using chronopotentiometery. We then evaluated the
performance of cathodes having a fixed Pt content, and two
different binders, over many feeding cycles in fed batch MFC
systems in terms of power densities and Coulombic ef-
ficiencies. We also compared the performance of the Pt-
containing cathodes to that of an inexpensive transition metal
based catalyst (cobalt tetramethylphenylporphyrin, CoTMPP)
using chronopotentiometery and in fed batch MFC tests.
Materials and Methods
Electrodes. The cathode electrodes used in electrochemical
cell tests had a projected surface area of 0.64 cm2, while both
electrodes used in MFC had a projected surface area of 7
cm2. Anodes were made of non-wet-proofed carbon cloth
(type A, E-TEK). For Pt-containing cathodes, a commercial
Pt catalyst (10 wt % Pt/C, E-TEK) was mixed with a chemical
binder (5% Nafion solution or 2% PTFE suspension) to form
a paste (7 L of binder per mg of Pt/C catalyst). The paste
was applied to one side of the wet-proofed carbon cloth (30
wt %, type B, E-TEK), and dried at room temperature for 24
h (Nafion) or at 350 C for 0.5 h (PTFE). The Pt content was
varied in the range of 0.1-2 mg cm-2 by changing the mass
of Pt catalyst used in the paste. Pt loadings less than 0.1 mg
cm-2 were not tested as it was not possible using our
application method to evenly apply the paste onto the
cathode at lower Pt loadings.
CoTMPP was also examined as an alternative to a Pt-
based catalyst as it has been demonstrated to have a high
activity for oxygen reduction in direct methanol fuel cells
(34). CoTMPP (Acros) was dissolved in chloroform (0.001 M)
and mixed with Vulcan XC-72 carbon (320 mg per 100 mL)
as previously described (35). The mixture was air-dried and
then heated in an inert-gas atmosphere at 800 C for 1 h. The
material (0.6 mg cm-2 CoTMPP loading) was applied to
carbon cloth using a Nafion binder by the same method
described above for the Pt catalyst cathode. A cathode
containing only carbon powder (Vulcan XC-72) was prepared
as a non-catalyst control.
MFC Tests. All MFC tests were conducted using single
chamber MFCs constructed as previously described (8), and
operated at a fixed external circuit resistance (1000 ). The
coated side of the cathode was placed facing the solution,
with the uncoated side exposed directly to air. MFCs were
inoculated using domestic wastewater (pH 7.3-7.6, chemical
oxygen demand (COD) ) 200-300 mg L-1) collected from
the primary clarifier of the Pennsylvania State University
Wastewater Treatment Plant. The wastewater was replaced
three to five times before the solution was switched to solution
containing glucose (1 g L-1) and a phosphate buffered nutrient
medium (PBM) containing NH4Cl (0.31 g L-1), NaH2PO4H2O
(4.97 g L-1), Na2HPO4H2O (2.75 g L-1), KCl (0.13 g L-1), and
a metal (12.5 mL) and vitamin (12.5 mL) solution (36). The
chamber was refilled each time the voltage decreased to less
than 50 mV, forming one complete cycle of operation. All
tests were conducted in a 30 C temperature-controlled room.
Glucose utilization was calculated on the basis of change
in COD, which was measured using standard methods (37).
All samples were filtered through a 0.22 m (pore diameter)
membrane filter prior to COD measurements.
Electrochemical Cell Tests. The cathode potential was
measured by applying a constant current in potentiometry
tests (chronopotentiometry; ref 38) using a three-chambered
electrochemical cell containing a working electrode (cathode
electrode with 0.64 cm2 projected surface area), a counter
electrode (platinum plate with a projected surface area of 2
cm2), and an Ag/AgCl reference electrode (EE009 no-leak
electrode, Cypress Systems). The catalyst-coated side of the
cathode was placed facing the solution, with the uncoated
side exposed directly to air. Chronopotentiometry studies
were conducted using a PC4/750 potentiostat (Gamry
Instruments) by applying a constant current for 60 min and
recording the stable value of the response potential. A curve
of the cathode potentials against current densities was used
to evaluate the performance of cathodes. For a fixed current
density, the higher the potential the better the performance
of the cathode material.
Calculations. Cell voltage was recorded using a multi-
meter and a data acquisition system (Model 2700, Keithly).
Current density in chronopotentiometry tests was calculated
as i ) I/A, where I (mA) is the applied constant current and
A (cm2) is the projected surface area of the electrode. Power
density in MFC tests was calculated according to P (mW
m-2) ) 10V2/(RA), where V (mV) is the voltage and R () is
the external resistance. Coulombic efficiency was calculated
as Ec ) Cp/Cth 100%, where Cp (C) is the total coulombs
calculated by integrating the current over time, and Cth is the
theoretical amount of coulombs available based on measured
COD removal in the MFC.
Results
Performance of Pt Cathodes with Different Pt Loadings
and Binders. To assess the effect of the Pt loading on their
performance at the current densities typical of MFCs,
electrodes were tested using chronopotentiometry at Pt
loadings ranging from 0.1 to 2 mg cm-2 with Nafion or PTFE
as the binder. At a Pt loading of 0.5 mg cm-2 (Nafion binder),
the cathode potential rapidly decreased from 307 to -239
mV for current densities up to 2 mA cm-2 (Figure 1A). These
potentials are much lower than those theoretically possible
under these solution conditions (620 mV vs Ag/Ag/Cl for 25
C at pH 7) or those theoretically possible in hydrogen fuel
cells under more acidic conditions and at higher temperatures
(1030 mV vs Ag/Ag/Cl, pH 0, 80 C) where the cathode is in
contact with a PEM and not water.
There was only a small change in the potential when the
Pt loading was changed within a range of 0.1-2 mg cm-2.
The difference in the potential of the other cathodes relative
to that of the cathode with a Pt loading of 0.5 mg/cm2 (E -
E0.5) was typically less than 10-20 mV (Figure 1A). Similar
results were obtained using PTFE as a binder for Pt loadings
of 0.25-1 mg cm-2 (Figure 1B). The potential decreased
rapidly from 288 to -257 mV at current densities up to 2 mA
cm-2. The potential differences (E - E0.5) of the cathodes
with various Pt loadings relative to that obtained at 0.5 mg
cm-2 Pt was generally less than 10-15 mV, or only a difference
of 4-10% in potential at a current density of 1 mA cm-2
(Figure 1B).
A comparison of the two different bonding materials at
a fixed Pt loading of 0.5 mg cm-2 showed that Nafion
produced slightly more positive potentials than PTFE when
compared at the same current density (Figure 2). For example,
at 1 mA cm-2, the measured potential with Nafion was 12%
more positive than that obtained using PTFE as the binder.
Performance of the CoTMPP Cathode. The performance
of a CoTMPP cathode (Nafion binder) was compared to Pt
VOL. 40, NO. 1, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 365

FIGURE 1. Cathode performance as a function of Pt loading measured
in the electrochemical cell using (A) Nafion or (B) PTFE binders.
The insets show the potential difference taking 0.5 mg cm-2 Pt
loading as reference.
catalyst cathodes (Nafion or PTFE binders) using chrono-
potentiometry. At current densities above 0.6 mA cm-2, the
potentials produced using CoTMPP were 3-15 mV more
positive than those using Pt and Nafion (Figure 2). At lower
current densities (<0.6 mA cm-2) the CoTMPP cathode
potential was up to 36 mV more negative than that obtained
with Pt (Nafion binder). Potentials produced with CoTMPP
were consistently more positive (1-35 mV) than Pt cathodes
using a PTFE binder (see inset in Figure 2). In all cases the
Pt and CoTMPP catalyst potentials were substantially more
positive than those obtained using a plain carbon cathode
(prepared in the same manner as the other cathodes, and
containing the carbon paste, but lacking a catalyst).
MFC Performance Using a Pt Catalyst with Different
Binders. The performance of the Pt catalyst (0.5 mg cm-2 Pt)
with a Nafion or PTFE binder was examined in MFCs operated
in a fed batch mode over 31 days (35 cycles). Following
acclimation, glucose was used as a substrate during the tests
with each cycle requiring 24 h before the voltage was
reduced to below <50 mV. The maximum voltage produced
with the Nafion binder varied between 0.5 and 0.6 V each
time the MFC was refilled, with this voltage generally
decreasing over time (Figure 3A). For example, the maximum
power density achieved in the MFC decreased from an
average of 480 ( 20 mW m-2 ((SD (standard deviation) based
on the averages of the maximum voltages for the first three
cycles; range of 464-508 mW m-2; Figure 3B) to 400 ( 10
mW m-2 (last three cycles; range of 390-414 mW m-2; Figure
3C). The current density ranged from 0.075 to 0.102 mA cm-2.
Although the maximum power density decreased, the Cou-
lombic efficiency increased during the same period from 8.9
( 0.4% to 18.6 ( 0.5% (Figure 3D).
366 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 40, NO. 1, 2006
When PTFE was used as the Pt (0.5 mg cm-2) binder on
the cathode, the maximum cell voltage was slightly lower
(<0.5 V) than that obtained with Nafion (Figure 4A). However,
the maximum voltage for each cycle did not decrease as much
over the operation period using PTFE as the binder as it did
with Nafion. The maximum power density for the PTFE
cathode with Pt decreased only 9%, or from 360 ( 10 mW
m-2 (cycles 2-4) to 331 ( 3 mW m-2 (last three cycles)
compared to a 19% decrease using Nafion (Figure 4B). The
Coulombic efficiency also varied over a smaller range during
the same period, or from 9.5 ( 1.5% to 13.1 ( 0.3%.
When the Pt loading was reduced to 0.1 mg cm-2 (Nafion
binder), the maximum power density of MFC averaged 340
( 20 mW m-2 (from 379 to 301 mW m-2) for 24 cycles of
operation (Figure 5A). These maximum power densities were
19% lower on average than those obtained with 0.5 mg cm-2
Pt and the same binder. The Coulombic efficiency ranged
from 4.5% to 7.5%, which is about half that obtained at the
higher Pt loading with a Nafion binder (Figure 5B).
MFC Performance Using a CoTMPP Cathode or in the
Absence of a Catalyst. In tests using CoTMPP as the cathode
catalyst, the power density was 369 ( 8 mW m-2 on average
(range from 397 to 361 mW m-2; 25 cycles), which is 12%
lower than that obtained with Pt (0.5 mg cm-2; Nafion binder)
(Figure 5A). The Coulombic efficiency ranged from 7.9% to
16.3% (Figure 5B), similar to that obtained with 0.5 mg cm-2
Pt and Nafion (Figure 3D).
In the absence of a cathode catalyst, the average power
density was reduced to 93 ( 13 mW m-2 (range from 104 to
88 mW m-2). This power density is 73% lower than that
obtained with Pt (0.1 mg cm-2; Nafion binder). The Cou-
lombic efficiency, however, was 10-20% lower than that
obtained with Pt (0.1 mg cm-2; Nafion binder) (Figure 5B).
Discussion
MFC tests at a fixed Pt loading (0.5 mg cm-2) demonstrated
that Nafion was a better binder than PTFE on the basis of
maximum power densities measured in 35 repeated fed batch
cycles. The maximum power density with Nafion averaged
480 mW m-2, while that obtained with PTFE was 14% less
at the same Pt loading. Reducing the Pt loading from 0.5 to
0.1 mg cm-2 (Nafion binder) produced a similar reduction
in power, averaging 19% less than that obtained at the higher
Pt loading. CoTMPP proved to be a suitable replacement for
Pt on the MFC cathode. In fed batch tests over many cycles,
the maximum power density using CoTMPP was actually
8.5% greater than that obtained at the lower Pt loading (0.1
mg/cm2) using a Nafion binder, and 5.4% greater compared
to that using a PTFE binder even at the higher Pt loading (0.5
mg cm-2 Pt). The maximum power with CoTMPP produced
only 12% less power than the Pt catalyst (Nafion binder) at
the higher Pt loading (0.5 mg cm-2). The Coulombic efficiency
of the CoTMPP was also similar to that obtained with the
higher Pt loading and Nafion binder, indicating that there
was greater overall conversion of substrate into electricity.
Chronopotentiometric tests were successful in predicting
the relational performance of the different catalysts and
binders, although the actual performance differences were
larger than the differences implied by the electrochemical
tests. On the basis of maximum power densities, the
performance of the different systems can be ordered ac-
cording to the following: 0.5 mg cm-2 Pt and Nafion binder
> CoTMPP > 0.5 mg cm-2 Pt and PTFE binder > 0.1 mg cm-2
Pt and Nafion binder > plain carbon electrode. This is the
same order expected from the chronopotentiometric tests at
current densities similar to that produced in the MFC tests
(<0.5 mA cm-2). Thus, chronopotentiometry tests were useful
as a rapid method of evaluating and ranking the different
electrode materials and preparation techniques.
FIGURE 2. Comparison of cathode potentials using Pt loading of
0.5 mg cm-2 and a chemical binder (Nafion or PTFE) compared to
a plain carbon cathode (no Pt, Nafion as a binder) and CoTMPP
cathode (Nafion as a binder). The inset shows the potential difference
taking 0.5 mg cm-2 Pt Nafion cathode as reference (except carbon
cathode).

FIGURE 4. Performance of the MFC with PTFE binder and Pt loading

of 0.5 mg cm-2: (A) cell voltage as a function of time and (B) power
density and Coulombic efficiency as a function of number of cycles.

FIGURE 3. Performance of MFC with Nafion binder and Pt loading

of 0.5 mg cm-2: (A) cell voltage over whole operation period; (B)
expanded view of cell voltage during first four filling cycles; (C)
cell voltage during last three cycles; (D) power density and
Coulombic efficiency as a function of number of cycles.

In general, there were larger differences in the maximum

power densities measured in MFC tests than those found for
the differences in potentials measured in choronopoten-
tiometric tests. In addition, there were changes in the
maximum power densities observed over time in MFC tests
that could not be anticipated from the chronopotentiometric
tests. Thus, some of the differences in maximum power
densities observed for the different catalysts and binders
during the MFC tests must result from other factors, such as
biofilm formation on the cathodes and the effects of chemicals
produced by the bacteria during glucose oxidation. Upon
completion of the MFC fed batch cycle tests, for example, it
was observed that the biofilm formed on PTFE cathode was
thin and loose compared to that formed on Nafion cathode.
While we cannot conclusively link this qualitative difference
in the biofilm to the performance of the two systems, we do
note that biofilm formation is a function of the hydrophobicity
of the surface (39-41). It seems that biofilm formation on
the cathode surface contributed to the increase in Coulombic
efficiency with the operation time of MFC according to the
results using different binders.
The function of a catalyst binder should not be confused
with the function of a PEM, although the same materials can
be used for both. Ideally, the main function of the binder is
FIGURE 5. Comparison of power densities (A) and Coulombic
efficiencies (B) achieved in MFCs containing different types of
cathodes. Numbers in parentheses in the legend indicate Pt loading
in mg cm-2.
to hold the catalyst in contact with the conductive electrode
surface, providing the catalyst as a site for the reaction of
oxygen, protons, and electrons. The purpose of a PEM is to
conduct protons from the anode to cathode. In an MFC,
water is the proton carrier between the electrodes. Removing
the PEM in an MFC can increase power (8), while the binder
may increase or decrease power depending on the nature of
the material. The lack of a PEM does reduce the Coulombic
efficiency compared to MFCs with a PEM, as previously noted
(8). The Coulombic efficiencies obtained here, while low, are

VOL. 40, NO. 1, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 367

consistent with values previously reported for this system (8,
14).
The relatively small effect of different Pt loadings on the
performance of MFCs is different from what could be
expected from hydrogen fuel cells, where the performance
is greatly affected by Pt loading. It has been reported that the
power density of a hydrogen fuel cell decreased by a factor
of 2 when the Pt loading was reduced from 0.387 to 0.074 mg
cm-2 (also using E-TEK materials, but with 40% Pt/C) (42).
These different results likely arise from the different operating
conditions of hydrogen fuel cells and MFCs, such as
electrolyte, temperature, and current density. For example,
the water content of the cathode in a hydrogen fuel cell is
controlled to prevent cathode flooding, while there is no
PEM in the MFC used here and the cathode is placed directly
in contact with water. Hydrogen fuel cells operate at higher
temperatures (50-80 C) and at current densities of 100 mA
cm-2 or more, while MFCs operate at much lower temper-
atures that bacteria can tolerate (30 C in the present study),
and produce current densities below 1 mA cm-2. Thus, it is
difficult to predict the magnitude of differences in these
systems produced solely by the materials used.
While it has been shown here that the performance of Pt
cathode with Nafion is better than that with PTFE, this
comparison does not consider the cost of these two chemicals.
Lowering the Pt loading by a factor of 5 reduced overall
performance by a factor of only 1.2, a difference that might
be acceptable given the cost of the catalyst and the large
surface areas needed for MFC operation. The CoTMPP
catalyst showed excellent promise as an alternative to Pt for
MFCs, but additional studies on loadings and long-term
stability of this material compared to Pt are needed. Thus,
further comparisons of the different cathode materials and
catalysts based on construction costs and long-term stability
are needed to better compare all aspects of using materials
in MFCs.
Acknowledgments
We thank Dr. Tom Mallouk for suggesting the use of the
CoTMPP material for the cathode. This research was sup-
ported by National Science Foundation Grants BES-0331824
and BES-0401885, a seed grant from The Huck Institutes of
the Life Sciences at Penn State, and the Stan and Flora Kappe
Endowment.
Supporting Information Available
Electrochemical cell used to examine cathode performance
as a function of Pt loading and chemical binder. This material
is available free of charge via the Internet at http://
pubs.acs.org.
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Received for review June 24, 2005. Revised manuscript re-
ceived October 17, 2005. Accepted October 18, 2005.
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