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i n t e rn a t i o n a l j o u rn a l o f h y d r o g e n en e r g y x x x ( 2 0 1 4 ) 1e9
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Treatment of domestic and distillery wastewater inhigh surface microbial fuel cells
Jayesh M. Sonawane a,b,1, Enrico Marsili c,d,e,f,*,Prakash Chandra Ghosh a,b,**,1
a Fuel Cell Research Facility, Department Energy Science and Engineering, Indian Institute of Technology Bombay,
Mumbai 400 076, Indiab IITB-Monash Research Academy, Indian Institute of Technology Bombay, Mumbai 400 076, Indiac School of Biotechnology, Dublin City University, Collins Avenue, Dublin 9, Irelandd National Centre for Sensor Research, Dublin City University, Collins Avenue, Dublin 9, Irelande Marine and Sensor Technology Hub, Dublin City University, Collins Avenue, Dublin 9, Irelandf Singapore Centre on Life Science Engineering (SCELSE), Nanyang Technological University, 637551, Singapore
a r t i c l e i n f o
Article history:
Received 17 April 2014
Received in revised form
25 June 2014
Accepted 17 July 2014
Available online xxx
Keywords:
Microbial fuel cell
Domestic wastewater
Distillery wastewater
Interlaced carbon yarn anode
* Corresponding author. Singapore Centre onTel.: þ65 6592 7895.** Corresponding author. Department EnergyTel.: þ91 22 2576 7896; fax: þ91 22 2576 4890
E-mail addresses: [email protected] Ghosh).
1 Tel.: þ91 22 2576 7896; fax: þ91 22 2576
Please cite this article in press as: Sonawcrobial fuel cells, International Journal o
http://dx.doi.org/10.1016/j.ijhydene.2014.07.00360-3199/Copyright © 2014, Hydrogen Ener
a b s t r a c t
Microbial fuel cells (MFCs) are bio-electrochemical devices that couple organic carbon
removal from wastewater and electricity production. Full-scale application of MFCs in a
wastewater treatment plant (WWTP) requires high surface, lowcost electrodes to maximize
microbial growth and power output. In this study, a high surface MFC anode is constructed
by interlacing carbon yarn with stainless steel. The anode is arranged in a double-air
cathode MFC configuration with 6 ± 1 U internal resistance. When closed on 100 U
external resistances in batch mode, the MFCs produce maximum power densities of
621 ± 17 and 364 ± 11 mW m�2 for domestic and distillery wastewater, respectively. The
chemical oxygen demand (COD) removal is 68% and 58% with a columbic efficiency of 47%
and 27% for domestic and distillery wastewater, respectively. The biofouling layer on the
Nafion membrane is twofold thicker in the domestic wastewater MFC, thereby suggesting
that the power output and COD removal in distillery wastewater MFC are not limited by the
cation transport across the membrane, but rather by the chemical composition of the
distillery wastewater that does not support an efficient electrochemically active microbial
community.
Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
Life Science Engineering (SCELSE), Nanyang Technological University, 637551, Singapore.
Science and Engineering, Indian Institute of Technology Bombay, Mumbai 400 076, India.., [email protected] (E. Marsili), [email protected], [email protected] (P.
4890.
ane JM, et al., Treatment of domestic and distillery wastewater in high surface mi-f Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.07.085
85gy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n en e r g y x x x ( 2 0 1 4 ) 1e92
Introduction
Microbial fuel cells (MFCs) convert chemical energy from
wastewater into electrical energy using viable electrochemi-
cally active microorganisms [1]. A typical MFC for energy re-
covery from wastewater is composed of an anodic chamber,
where the organic matter in the wastewater is oxidized by the
microbial biomass, and a gas-porous air cathode where at-
mospheric oxygen is reduced [2]. Other MFC architectures
have been designed to couple chemical oxygen demand (COD)
reduction with removal of nitrate [3], azo dyes [4], and drug
residues [5].
The power output of wastewater MFC depends on
numerous factors, including the concentration of electro-
chemically active microorganisms [6], cathode and
anode electrode assembly [7,8], the composition and the
thickness of the ion-selective membrane between the two
electrodes [9], the reactor design [10], the organic load, the
Fig. 1 e A schematic design of the MFC used in this study: (a) M
overall experimental setup.
Please cite this article in press as: Sonawane JM, et al., Treatmecrobial fuel cells, International Journal of Hydrogen Energy (2014
operating temperature, and the value of external resistance
(Rext) [11].
Reactor cost and operative costs should be considered for
scale-up and practical application in WWTPs [12]. Recent
research has singled out reactor configurations that allow
high energy recovery when used in conjunction with actual
domestic or industrial wastewater. For example, a low-cost,
tubular MFC stack removed more than 90% of COD and 80%
of total nitrogen from domestic wastewater [13]. Tubular
MFCs installed in municipal wastewater remove 65e70% of
the initial COD, although sulphate reduction scavenges elec-
trons and reduces the overall power output [3]. High surface
anode materials, like carbon based sponges, cloths, and fibres
increase immobilisation of electrochemically active microor-
ganisms, which have resulted in power output improvement
[14]. However, the scale-up of high surface MFCs is not
straightforward. For example, MFCs based on high surface
graphite brush anode produce 75e150 Wm�3 power output at
laboratory conditions, but freely floating graphite fibres
FC assembly; (b) details of interlaced yarn anode; and (c)
nt of domestic and distillery wastewater in high surface mi-), http://dx.doi.org/10.1016/j.ijhydene.2014.07.085
i n t e rn a t i o n a l j o u rn a l o f h y d r o g e n en e r g y x x x ( 2 0 1 4 ) 1e9 3
require supporters to maintain the shape of larger electrodes
[15]. Increasing the anode surface with nanoparticles or
implanting functional groups by plasma or chemical treat-
ment determines rapid biofilm attachment and fast electron
transfer rate at the interface biofilm/electrode [16e17].
However, as the anodic biofilm grows, the anode surface is
covered and the biofilm layer close to the bulk liquid show
slower electron transfer rate than those closer to themodified
surface [18].
To achieve high power output, internal resistance Rint
should be very low. Dense biofilms formed by rod shaped
microorganisms have Rint as low as 10 U [19], whereas mi-
croorganisms on the high surface anode that are based on
graphite brush have Rint as low as 8 U [20]. These designs
provide efficiency at the laboratory scale and may be suitable
for pilot-scale or large-scale implementation like retrofitting
of existing WWTPs.
Despite these recent results, there is still a need for high
surface MFC assemblies that are suitable to treat raw waste-
water with minimal pretreatment. This study reports an
anode design based on interlaced carbon yarn that provides a
large accessible surface for biofilm attachment and is suitable
for the scale-up and deployment in conventional WWTP. The
cell was equipped with a double air-breathing cathode to
minimize cathode limitations and to further increase the
power output.
Materials and methods
Microbial fuel cells configuration
Two identical MFCs with interlaced carbon yarn anode and
porous air cathodes were fabricated with 0.8 cm thick acrylic
sheet (Fig. 1(a)). Each MFC had a 0.7 L anodic chamber
(12.5� 7� 8 cm)with two openings on the front and rear sides,
where two identical air cathodesweremounted, plus inlet and
outlet for recirculation and sampling. Recirculation at a rate of
0.45 L min�1 was achieved by a mini fountain pump and the
recirculated wastewater was evenly distributed in the vicinity
of the cathodes.
Electrode fabrication
The anodewas designed using a perforated stainless steel (SS-
308) sheet, which was folded to form a frame with a dimen-
sion of 12.2 � 6.7 � 7.7 cm. The 0.2 cm thick carbon yarn was
purchased at 12 USD/Kg (Y2100, Aiflon, China) and was woven
alternately through the holes on the SS sheet in horizontal
and vertical threading (Fig. 1(b)), leading to a projected anode
surface of 0.1018 m2. The interlaced carbon yarn anode as-
sembly was placed in the anode chamber and connected with
the electrical circuit through two stainless steel rods.
Nafion NE 1135 (thickness 89 mm) was used as cationic
exchange membrane. The cathodes were fabricated adapting
a previously described method [21]. In brief, fine platinized
Vulcan XC-72carbon powder (Pt content 20% wt.) (Sigma
Aldrich, India) was coated on a 12.5 cm � 8 cm Toray TGP-H-
060 carbon Paper (Fuel Cell Etc., USA), to fabricate the cath-
ode. The platinum loading in the electrode was 0.5 mg cm_2
Please cite this article in press as: Sonawane JM, et al., Treatmecrobial fuel cells, International Journal of Hydrogen Energy (2014
using 5%wt. Nafion solution as a binder (SigmaAldrich, India).
Subsequently, the electrode was hot-pressed on one side of
89 mm Nafion NRE-1135 (Sigma Aldrich, India) under
10 kg cm�2 pressure at 140 �C for 2 min. The resulting mem-
brane electrode assembly was then inserted in the MFC. Two
identical membrane-cathode assemblies were mounted in
each MFC (Fig. 1(a)). The cathodes were connected to the
external electrical circuit through silver paste and copper
wires (Fig. 1(c)).
Inoculation of MFCs
One of the MFCs was fed with domestic wastewater, the
other with distillery wastewater. The experiments were
conducted simultaneously at ambient temperature. The
initial pH and COD of domestic wastewater collected from
the primary clarifier of the Mumbai municipal WWTP were 8
and 1650 mg L�1, respectively. Secondary treated distillery
wastewater with pH 7.8 and COD 2303 mg L�1 was obtained
from a local distillery. The relatively low COD value for the
distillery wastewater might be due to abundant rains in the
days before wastewater collection. Each wastewater amount
was divided in three jars, which were maintained at 4 �Cprior to the inoculation in the MFC. At the beginning of each
cycle (three cycles for each wastewater, for a total of six
experiments), the wastewaters were sparged with N2 for
30 min prior to inoculation, and the MFCs were sparged for
10 min after inoculation, to increase the initial activity of
obligate anaerobes and minimize aerobic oxidation of
organic matter.
Operation of MFCs
The temperature of the anodic compartment was measured
by a thermocouple. The ambient temperature varied between
23 �C in the night and 33 �C in the day. Such temperature
variation is typical of MFC run in tropical environment with
no temperature control. However, the current output in
the week-long experiments did not change significantly
within a day, likely because the mixed microbial consortia in
the MFC was adapted to these variation of temperature. Both
the MFCs were operated for three different cycles of 7e8 days
duration. In the first cycle, the Rext was disconnected and the
open circuit potential (OCV) was recorded. The first run
ensured the acclimatization of the inoculum and the forma-
tion of a healthy biofilm on the anode surface. Following
removal of spent wastewater, the MFCs were re-inoculated
with new wastewater and closed on a 100 U Rext. The polar-
isation curveswere recorded under recirculating and stagnant
conditions on day 3 and 4, respectively. The third cycle was
carried out with recirculation and the polarisation curves
were recorded on day 3.
Analytics and calculations
COD concentration in each cell was measured daily. The two
cathodes were connected to the common anode and the MFC
potential was continuously monitored in a two-electrode
mode every 10 min using a data logger (Graphtec GL800,
Japan). The values of the potential were averaged on 36 data
nt of domestic and distillery wastewater in high surface mi-), http://dx.doi.org/10.1016/j.ijhydene.2014.07.085
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n en e r g y x x x ( 2 0 1 4 ) 1e94
points (6 h). The current output was calculated by Ohms' lawacross the Rext [22]. The power density, normalised to the
projected cathode surface area, was calculated by P ¼ E2/
(Rext.A), where A [m2] is the projected cathode surface, Rext [U]
the external resistance, E [Volts] the MFC potential. The
polarisation curve was obtained by changing the Rext step-
wise from 100 U to 1 U. Each value of the Rext was main-
tained for 15 min and the total procedure required 6 h. The
internal resistance of the MFCs was measured through elec-
trochemical impedance spectroscopy (EIS) with a potentiostat
(VSP, Bio-Logic, France) and the slope of the polarization
curve, as previously described [22]. The EIS measure were
conducted in three-electrode configuration, with a Ag/AgCl
reference electrode inserted in the anodic chamber.
The CODwasmeasured through standardmethod [23]. The
cumulative COD removal efficiency and the Coulombic effi-
ciency h were calculated as previously described [22]:
DCODcu
�t
�¼ COD0 � CODðtÞ
COD0� 100 (1)
where DCODcu% (t) [mg L�1] is the cumulative COD removal
efficiency at time t, COD0 [mg L�1] is the initial COD and COD (t)
[mg L�1] is the COD at time t;
h�t� ¼
MZ t
0
idt
F$n$V$DCODcuðtÞ (2)
Fig. 2 e SEM images of the well-developed anodic biofilm imm
magnification. Panel (b) shows microorganisms not embedded
domestic wastewater MFC at (c) 1000£ and (d) 10000£ magnifi
extracellular polymeric matrix is more abundant than in distill
Please cite this article in press as: Sonawane JM, et al., Treatmecrobial fuel cells, International Journal of Hydrogen Energy (2014
where M [g] ¼ 32 is the molecular weight of O2, F [C
(Me�)�1] ¼ 96,485 is Faraday's constant, n ¼ 4 is the number of
electrons exchanged per molecule of oxygen reduced, and V
[L] ¼ 0.7 is the anode volume.
Scanning electron microscopy
A small section of each anode with the electrochemically
active biofilm was prepared for electron microscopy by fixing
the electrode piece in 3% glutaraldehyde buffered with 0.1 M
phosphate buffer at room temperature for 24 h. After fixation,
the sample was rinsed with a the same buffer, and then
dehydrated step-wise with 30%, 40%, 50%, up to 100% in
ethanol, for 15 min at each ethanol concentration. Samples
were mounted on aluminium stubs, sputtered with gold and
examined in a DSM 940A (Zeiss, Germany). The resolution
range used for microscopy varied from 700� to 3000�. At the
end of the experiments, the dry Nafion membranes were
mounted on aluminium stubs, sputtered with platinum, and
examined by energy dispersive spectroscopy (EDS) in the
scanning electron microscope (SEM).
Results
The OCV for bothMFCs reached themaximumvalue of 788 ± 3
and 516 ± 5 mV 6 h after inoculation. However, the OCV of the
distillery wastewater MFC decreased rapidly with time,
ersed in distillery wastewater (a) 1000£ and (b) 10000£in extracellular polymeric matrix. Anodic biofilm from
cation. Electrode coverage is less homogeneous and
ery wastewater biofilm.
nt of domestic and distillery wastewater in high surface mi-), http://dx.doi.org/10.1016/j.ijhydene.2014.07.085
i n t e rn a t i o n a l j o u rn a l o f h y d r o g e n en e r g y x x x ( 2 0 1 4 ) 1e9 5
indicating fast depletion of organic carbon substrate (Fig. 3).
Following MFC treatment, the color of distillery wastewater
changed from dark brown to malt brown. When closed on a
100 U Rext in the second and third cycles, the domestic
wastewater MFC exhibited a similar sustainable current of
approximately 297.1 ± 3.8 and 298.1 ± 2.8 mA m�2 for six days
until substrate depletion occurred on day seven (Fig. 4(a)).
The sustainable power produced from the domestic
wastewater MFC was 170.3 ± 1.5 mW m�2. However, the
maximum current and power in the short-term polarization
curves was recorded at Rint ¼ 6 U is 2204 ± 30 mA m�2 and
621 ± 17 mW m�2, respectively, with little difference between
the second and third cycle (Fig. 5(a)). The maximum power
output under stagnant conditions was approximately 20%
lower, indicating that diffusional limitations have a limited
effect when Rext ¼ 100 U.
The difference between the short-term maximum power
output and the sustainable power output indicated that the
MFC could be operated sustainably at lower Rext [24]. The
sustainable current output of the distillery wastewater MFC
was 261.4 ± 12.7 mA m�2, without significant difference be-
tween the two cycles. The sustainable power output was
128.1 ± 6.2 mW m�2. Differently from the domestic waste-
water MFC, the current output was less stable and decreased
rapidly after two days (Fig. 4(b)). The maximum current and
power output at Rint ¼ 6 U were 1815 ± 189 mA m�2 and
364 ± 11 mW m�2, respectively (Fig. 5(b)).
The power output determined from both polarization and
one-week experiments were higher for the domestic waste-
water MFC, despite the higher COD concentration in distillery
wastewater. This finding confirms that COD concentration
alone does not allow estimation of power production in any
given wastewater, although it serves for rapid comparison
Fig. 3 e Open circuit potential (OCV) for distillery
wastewater and domestic wastewater MFCs. OCV remains
approximately constant in domestic wastewater, while the
OCV of distillery wastewater decreases nearly 30% over
seven days, likely because of partial COD removal by non-
electrochemically active microorganisms. Low OCV value
confirms that distillery wastewater is not an optimal
substrate for bioelectricity production.
Please cite this article in press as: Sonawane JM, et al., Treatmecrobial fuel cells, International Journal of Hydrogen Energy (2014
between different MFCs fed with the same wastewater. It is
also likely that distillery wastewater contains a small alcohol
concentration and trace of toxic chemicals that might inhibit
electrochemically active microorganisms.
Anodic biofilms
The carbon fibres of the anode are colonized by biomass after
24 days (Fig. 2). The biofilm in the domestic wastewater MFC is
less dense and distributed in large clusters, while part of the
fibres appears free from biomass (Fig. 2(a)). The biofilm on the
anode of distillery wastewater MFC covers most of the carbon
fibre surface (Fig. 2(c)). The biofilm matrix in the domestic
wastewater MFC is more evident than in the distillery MFC
(Fig. 2(c)). Individual cells were observed only in the distillery
wastewater MFC (Fig. 2(d)). As the matrix of electrochemically
active biofilms is usually conductive [25], the lower concen-
tration of biofilm matrix in the distillery wastewater MFC
might explain the lower power output of the latter with
respect to the domestic wastewater MFC.
COD removal and coulombic efficiency
The cumulative COD removal was 74.3 and 57.8% with a h of
47% and 27% for domestic and distillery wastewater, respec-
tively. The cumulative COD removal and the h were plotted in
Fig. 6(a and b), respectively. The COD removal rate decreased
in the last five days for distillery wastewater. As both MFCs
were operated at Rext higher than the maximum sustainable
resistance, it was likely that COD removal rate can be
improved by lowering Rext. The h increased with time for both
MFCs, indicating adaptation of the electrochemically active
consortia. The low h for distillery wastewater confirmed the
prevalence of fermentative microbial over electrochemically
active consortia at the anode.
Biofouling layer and elemental composition
The biofouling of the Nafion membranes at the end of the
three cycleswas characterised by Zeta 2Dmicroscopy (Fig. S1).
The average thicknesses of the biofouling layers were
approximately 30 mm and 60 mm in distillery and domestic
wastewater, respectively (Fig. S1(a and b)). The effect of the
biofouling layer was evident in the mass transfer-limited re-
gion of the polarisation curve, where the cell potential of the
domestic wastewater MFC (Fig. 5(a)) decreased faster than the
in the distillery wastewater MFC (Fig. 5(b)). Interestingly, the
mass transfer limitation region of the domestic wastewater
MFC (Fig. 5(a)) overlapped partially with the maximum power
output region, indicating that the biofouling layer should be
reduced to increase the power output of the system.
Conversely, the organic load or the flow rate of the distillery
wastewater MFC can be further increased before the power
output is controlled by the mass transfer at the cationic
membrane.
During the operation of the systems, bacterial debris and
suspended solids settled on a Nafion membrane and formed
multiple layers. SEM-EDS analysis showed that the elemental
composition of the biofouling layers were different for do-
mestic and distillery wastewater (Fig. S2). The carbon content
nt of domestic and distillery wastewater in high surface mi-), http://dx.doi.org/10.1016/j.ijhydene.2014.07.085
Fig. 4 e (a) Current density in the domestic wastewater MFC at Rext ¼ 100 U. The current output is similar in both 2nd and
3rd cycle and it remains constant for about six days, indicating that the Rext is sustainable; (b) current density in the
distillery wastewater MFC at Rext ¼ 100U. The current output is similar in 2nd and 3rd cycle, and it decreases following MFC
inoculation.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n en e r g y x x x ( 2 0 1 4 ) 1e96
was higher on the membrane exposed to distillery waste-
water, as expected from the higher COD concentration with
respect to domestic wastewater. Trace metals were found on
the membrane exposed to domestic wastewater. This may
partly explain its better performance as opposed to the dis-
tillery wastewater MFC, as trace metals are needed for the
overall fitness of the electrochemically active microbial
consortia.
Discussion
The first cycle under OCV conditions ensures the formation of
active biofilm on the anode. It is well-known that transfer of
anodic biofilm from already exposed to electrogenic condi-
tions shortens acclimation time and speeds up power output
production [26,27]. However, acclimation time decreases also
when biofilm grown under non-electrogenic conditions is
Fig. 5 e (a) Polarization curves of the domestic wastewater MFC
obtained at Rext ¼ 6 ± 1 U. Recirculation of the anolyte increase
distillery wastewater MFC. The maximum power output of abo
Please cite this article in press as: Sonawane JM, et al., Treatmecrobial fuel cells, International Journal of Hydrogen Energy (2014
exposed to anodic potential [28]. In this study, power output
started immediately after replacement of spent wastewater
with fresh wastewater and exposure to anodic potential.
The biosolids contained in domestic wastewater deposited
on the MFC anode and on the cationic membrane, resulting in
a complex biofilm structure. On the other hand, the biofilm
observed in the anode and cationic membrane immersed in
distillery wastewater show lower biosolids concentration. It is
likely that the different power output of the two MFCs studied
here is due to the different microbial ecology of the anodic
communities. A recent study on high-strength synthetic
wastewater MFCs show biofilm formation on the electrodes
and the membrane [29]. The presence of numerous metals
and oligo-nutrients on the domestic wastewater MFC mem-
brane suggests that the microbial community in this MFC can
harbour a larger concentration of electrochemically active
bacteria, which result in a higher power output. A recent study
on MFC fed with high-strength molasses wastewater shows
. The maximum power output of about 600 mW m¡2 is
s power output of about 20%; (b) polarization curves of the
ut 350 mW m¡2 is obtained at Rext ¼ 7 ± 1 U.
nt of domestic and distillery wastewater in high surface mi-), http://dx.doi.org/10.1016/j.ijhydene.2014.07.085
Fig. 6 e Energy recovery from domestic and distillery wastewater: (a) cumulative COD removal at Rext ¼ 100 U; the COD
removal is faster in the domestic wastewater MFC; (b) the coulombic efficiency is much higher in the domestic wastewater
MFC.
i n t e rn a t i o n a l j o u rn a l o f h y d r o g e n en e r g y x x x ( 2 0 1 4 ) 1e9 7
that most of the bacteria present in the inoculum are also
found in the biofilm after 5-months operation. The enrich-
ment in electrochemically active strains however was not
fully demonstrated [30].
The Rint is probably the single most important electrode
parameter for power output [19]. The Rint of a MFC depends
upon the electrode material [31], electrode spacing, and
system architecture [32]. A recent review on microfluidic
MFCs analyses the adverse effects of internal resistance on
power production in MFCs and show that electrode topology
and electrode surface area/volume ratio [19]. The Rint
calculated by the slope of the polarization curve
was7.3 ± 0.3 U and was dependent on the wastewater used
or the recirculation conditions. The Rint calculated from
impedance data was 6 ± 1 U, thus inferring the two methods
are in good agreement. The low Rint measured in this MFC
assembly is very promising for effective energy recovery
from wastewater.
The two wastewaters tested in this study yielded very
different power output and, most importantly, showed the
different power output as a function of time. In fact, domestic
wastewater produces a near-constant power output, while the
Table 1 e Comparison with other MFCs with distillery and dom
WW Reactor vol.(mL)
pH Anode Cat
Distillery 501 6 Graphite plate Graphi
7270 7e8 Carbon paper Carbon
700 7.8 Interlaced carbon yarn Carbon
Domestic 28 e Carbon paper Carbon
28 e Carbon paper Carbon
21 7.5 Carbon cloth Carbon
150 7 CNT sponge CNT sp
700 8 Interlaced carbon yarn Carbon
Synthetic 26 e Graphite fibre brush-small
(C-MFC)
Carbon
300 e Graphite fibre brush-large
(B-MFC)
Carbon
Please cite this article in press as: Sonawane JM, et al., Treatmecrobial fuel cells, International Journal of Hydrogen Energy (2014
power output of the distillery wastewater MFC decreases
rapidly with time. This unusual behaviour of distillery
wastewater MFCs has not been observed in previous litera-
ture, where continuous flow MFCs were used [19,33,34]. It
should be noted that distillery wastewater produces a low
power output despite its high COD. Biological oxygen demand
(BOD) should be used instead of COD to obtain a meaningful
correlation between bioavailable substrates and power
output.
Microorganisms rapidly foul cationic exchange mem-
branes during MFC operations. After 90 days, fouling slows
down cation diffusing, thus increasing pH gradient and the
corresponding potential loss, which in turn decreases the
maximum power output to 30% in a synthetic wastewater
MFC. The fouling layer was composed of attached microor-
ganisms and inorganic salts precipitated from the anodic
medium. However, the thickness of the fouling layer was
not measured [33]. Long-term membrane fouling (250 days)
reported more than 50% decrease in power output of mi-
crobial desalination cells. The fouling seems to affect pref-
erentially cationic over anionic exchange membranes [35].
However, biofouling may be an indirect indicator of
estic wastewater as a substrate.
hode Max. power density(mW/m2)
COD removal(%)
Reference
te plate 124 72.8 [33]
paper 124 80e90 [34]
paper 348 57 Present work
paper 72 42 [41]
cloth 103 71 [42]
cloth 464 89e93 [21]
onge 1240 90 [16]
paper 594 68 Present work
cloth 2400 e [20]
cloth 1430 e [20]
nt of domestic and distillery wastewater in high surface mi-), http://dx.doi.org/10.1016/j.ijhydene.2014.07.085
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n en e r g y x x x ( 2 0 1 4 ) 1e98
membrane efficiency. In fact, a study on membrane fouling
in two-chamber synthetic wastewater MFCs showed that
the internal resistance of a Nafion membrane is due not to
biofouling but to the increase of other cations from the
anodic solution replacing the sulfonate groups of the
membrane [36].
The results presented here show that membrane fouling is
much higher in the membrane exposed to domestic waste-
water than in that exposed to distillery wastewater. However,
the Coulombic efficiency in the earlier is higher than in the
latter, suggesting that cation transfer across the membrane is
not a rate-limiting step for the overall energy conversion
process.
Energy recovery from distillery wastewater varies
depending on its actual chemistry (raw or partially degraded)
and the MFC configuration. Post-methanation distillery
wastewater yields 0.5 W m�3 in two-chambered MFC [37] A
continuous flow two-chambered- MFCs fed with raw distillery
wastewater removed 80e90% of the influent COD with
124 mW m�2 of power output [38]. Two-chambered thermo-
philic MFCs with graphite-felt electrodes produce nearly
1 W m�2 when fed with distillery wastewater with ~80% COD
removal and ~80% Coulombic efficiency [29]. The power
output of the MFC presented here is comparable to those re-
ported in previous studies (Table 1).
Treatment of distillery wastewater is routinely carried
out with fungal treatment. A recent study reports 61%
color removal and 65% COD removal in approximately 14 days
[39]. Extracellular ligninolitic enzymes secreted by fungi
are the main responsible for distillery wastewater decolouri-
zation [40].
Conclusions
Batch MFCs with interlaced carbon yarn anode and air-
breathing cathode were used to treat raw domestic and dis-
tillery wastewaters. The recorded power output of
621 ± 17 mW m�2 for domestic wastewater is consistent with
previous MFC studies. However, the power output measured
for distillery wastewater was much lower, 364 ± 11 mW m�2.
Coulombic efficiency and COD removal were much higher for
the domestic wastewater MFC than the distillery wastewater
MFC. Analysis of the biofouling layer on the Nafionmembrane
showed that the low energy recovery from distillery waste-
water at Rext ¼ 100 U was not due to cation diffusional limi-
tations through the membrane. The rapid decrease of current
with time in the distillery wastewater MFC suggests that dis-
tillery wastewater alone does not support efficient electro-
chemically active microbial communities.
Acknowledgements
Enrico Marsili was supported by the EU-FP7 Marie Curie In-
ternational Reintegration Grant P.N. 231072.We thank Amruta
Bhave for her help with MFC operation and Dr Sharon Long-
ford and Dr Seratna Guadarrama for their help with the edit-
ing of the manuscript.
Please cite this article in press as: Sonawane JM, et al., Treatmecrobial fuel cells, International Journal of Hydrogen Energy (2014
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.ijhydene.2014.07.085.
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