Fuel 140 (2015) 209216

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Characterization of light/dark cycle and long-term performance test in a

photosynthetic microbial fuel cell
Araceli Gonzalez del Campo a,, Jose F. Perez a, Pablo Caizares b, Manuel A. Rodrigo b,
Francisco J. Fernandez a, Justo Lobato b
a

University of Castilla-La Mancha, Chemical Engineering Department, ITQUIMA, Av. Camilo Jos Cela S/N, 13071 Ciudad Real, Spain
University of Castilla-La Mancha, Chemical Engineering Department, Faculty of Chemical Sciences & Technologies, Building Enrique Costa Novella, Av. Camilo Jos Cela S/N,
13071 Ciudad Real, Spain
b

h i g h l i g h t s
 A photosynthetic microbial fuel cell was used to recover energy of wastewater.
 Light/dark cycle in a photosynthetic microbial fuel cell was characterized.
 When dissolved oxygen was low, nitrate and sulfate could be used as electron acceptor.
 The system showed a great reliability and durability.

a r t i c l e

i n f o

Article history:
Received 20 March 2014
Received in revised form 18 August 2014
Accepted 23 September 2014
Available online 7 October 2014
Keywords:
Photosynthetic microbial fuel cell
Light/dark cycle
Electron acceptor
Life test

a b s t r a c t
In this paper, the characterization of light/dark cycle in a photosynthetic microbial fuel cell used to
recover energy of wastewater was carried out. To this end, a wide range of parameters were measured
throughout both periods light/darkness. During the light phase, the electricity production was higher
because algae carried out photosynthesis and produced oxygen, which acted as electron acceptor.
However, during the dark phase, electricity was still on production when dissolved oxygen at the cathode
was nearly zero, indicating that nitrates and sulfates (added as nutrients to the cathode) were also acting
as electron acceptors. COD and nutrients removal at the anodic compartment was found constant all day
and about equal to 75% (COD removal), 70% (ammonium removal) and 26% (phosphate removal). The
highest value of maximum power density (42.98 mW m2) and the lowest value of internal resistance
(1680 O) were reached at 13:00 h. The polarization resistance of the cathodic compartment changed during the day as a function of the cycle of light/dark, between 6930 O and 13210 O. Finally, a life test was
carried out for 10 months, demonstrating an adequate performance in terms of durability and reliability.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Energy demand is steadily on the rise, as a consequence of the
growing population and higher living standards. A high percentage
of this energy is supplied by fossil fuels, which unfortunately contribute to the global warming. Ideally, new energy sources should
preferably be renewable and carbon-neutral.
On the other hand, wastewaters must be treated for both
complying with the law and avoiding harms to the environment.
Up to know, all the processes used in wastewater treatment are
energy-consuming. It was estimated that 1.5% of the total energy
produced in U.S.A. is consumed in wastewater treatments [1].
Corresponding author. Tel.: +34 926 295300x96319; fax: +34 926 295242.
E-mail address: Araceli.gdelcampo@uclm.es (A. Gonzalez del Campo).
http://dx.doi.org/10.1016/j.fuel.2014.09.087
0016-2361/ 2014 Elsevier Ltd. All rights reserved.

Considering the aforementioned reasons, new sources of energy

are under investigation. In particular, energy recovery technologies
from biomass-rich wastewaters, using microorganisms, are a topic
of current interest in scientic discussions [24].
Certain technologies, such as Microbial Fuel Cells (MFCs), can
approach successfully energy production and wastewater treatment at the same time. MFCs are bioelectrochemical systems
(BESs) which convert chemical energy into electric using microorganisms [5]. In an MFC, a substrate (often organic matter) is
oxidized in a type of biological process in which microorganisms
deliver electrons to an anode surface [6]. The electrons ow
through an external load (electrical current) and they are released
at the cathode, where a reaction between electrons and electron
acceptors take place [1,7].

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A. Gonzalez del Campo et al. / Fuel 140 (2015) 209216

The usual MFCs set-up consists of two chambers (anodic and

cathodic) separated by a proton exchange membrane (PEM). Until
recently, just half of the system, the anode, was biological. But
lately, full-biological set-ups have been studied using microorganisms at the cathode, so-called biocathode [8]. These systems
present major advantages over abiotic or chemical cathodes.
Among them, lower investment and operating costs (added catalysts may not be necessary since microorganisms are the actual
ones) as well as the possibility of taking advantage of other metabolic pathways to remove pollutants or produce any other product
of interest at the cathode [9].
A possible classication for biocathodes is according to the terminal electron acceptor used in the cathodic reaction: oxygen (i.e.
aerobic) or non-oxygen (i.e. anaerobic). In absence of oxygen
(anaerobic), other molecules can function as terminal electron
acceptor: nitrate, sulfate, selenate, arsenate, carbon dioxide or oxidized metal ions like iron and manganese [10]. Among all the electron acceptors, oxygen (aerobic) is the most popular for the
cathodic reaction in MFCs. Basically, due to its high redox potential
and abundance in the atmosphere resulting in relatively low cost
of supply. However, aeration costs mean approximately 50% of
the whole operating costs [11]. Furthermore, sunlight can be used
through photosynthetic microorganisms in a MFC. If so, the system
is known as photosynthetic MFC. There are many possible congurations of photosynthetic MFCs [12]. In particular, photosynthetic oxygen production is quite interesting to provide the
terminal electron acceptor, oxygen, avoiding the need for pumping
and its subsequent energy costs.
In this experimental set-up, a biocathode containing algae
Chlorella vulgaris for oxygen production was used. Since algae are
photosynthetic microorganisms, oxygen is only produced when
they are exposed to sunlight causing two different periods in the
system: light and darkness. In this work, a two-chambered photosynthetic MFC for energy production was under study. A wide
range of parameters was measured throughout both periods
light/darkness so that the behavior of the system was characterized. To nish up, important characteristics such as endurance
and reliability of the system was tested, making use of a long-term
life-study.

2. Experimental
2.1. Experimental set-up
The photosynthetic microbial fuel cell used in this study, Fig. 1,
consisted of a biological reactor separated into two identical chambers (800 mL each) by a proton exchange membrane (PEM, by
Sterion) [1315]. In each compartment, Toray carbon cloths with
10% of Teon were used as electrode. Noble metal was not used as
catalyst in the electrodes. The active area of each electrode was
8 cm2. Under normal working conditions, the anode and the cathode were connected by means of wires and an external resistance
of 120 O.
The initial inoculum was an activated sludge from a conventional domestic wastewater treatment plant described elsewhere
[16], after 25 days a biolm of microorganisms was formed on
the surface of the anodic electrode [15]. It was fed in continuous
mode with 1.23 mL min1 of synthetic urban wastewater, which
contained 322 mg L1 of organic matter (161 mg L1 of glucose
and 161 mg L1 of fructose) and nutrients. The composition of
the wastewater was shown in a previous paper [15].
The cathode compartment contained an initially pure culture of
Chlorella vulgaris to supply oxygen. The articial solar energy was
supplied (11.5 h per day, from 9:00 h to 20:30 h) with an 11 W
Fluorescent lamp (Philips) with an illumination intensity of

Fig. 1. Picture of the set-up.

2.7 cd cm2. CO2 was used as an inorganic carbon source for algae,
therefore, every day CO2 was bubbled at the cathodic compartment
during 30 min. In this way, the cathodic compartment can act as
carbon sink. Moreover, the algae were fed with a Bolds basal medium [17]. The temperature in both compartments was 26 1 C.
A Keithley 2000 Digital Multimeter was connected to the system to monitor continuously the cell voltage. The cell was placed
over a multipoint magnetic stirrer in order to keep the anodic
and cathodic compartment in suspension and improve the matter
transfer. Oxygen concentration was continuously monitored in the
cathodic compartment with an Oxi538 WTW oxymeter.
2.2. Characterization techniques
In both compartments, conductivity and pH were measured
with a Jenway 740 conductometer and a PCE-228 pH meter,
respectively. Chemical oxygen demand (COD) was determined by
photometric method with MERCK COD cell test and Pharo 100
MERCK spectrophotometer.
Anions were measured by ion chromatography using Shimadzu
LC-20A equipment (column, Shodex IC I-524A; mobile phase, 2.5 m
Mphthalic acid at pH 4.0; ow rate, 1.0 mL min1). The same ion
chromatography equipment (column, Shodex IC YK-421; mobile
phase, 5.0 mM tartaric, 1.0 mM dipicolinic acid and 24.3 mM boric
acid; ow rate, 1.0 mL min1) was used to measure cations [18].
Polarization curves were recorded using an Autolab PGSTAT30
potentiostat/galvanostat (Ecochemie, The Netherlands) at a scan
rate of 0.5 mV s1 and a step potential of 1 mV. These curves make
it possible to discern three key parameters: the open circuit voltage (OCV), maximum power density (Pmax) and internal resistance
[15]. In addition, analyzing the plot, the limiting processes which
control the performance of the cell can be identied [19,20]. The
main source of error in the characterization techniques used in this
work came from the intrinsic variability in the behavior of the
microorganisms of the biolm, due to their changing nature [21].
The same potentiostat/galvanostat (Autolab PGSTAT30, Ecochemie, The Netherlands) using the frequency response analyser (FRA)
module was used to carry out electrochemical impedance spectroscopy (EIS). EIS measurements were run for the full cell at open
circuit conditions, in a frequency range of 10 kHz1 mHz and with

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A. Gonzalez del Campo et al. / Fuel 140 (2015) 209216

In order to study and understand the behavior of the photosynthetic MFC, some operational variables were monitored throughout the day during one week (7 consecutive days). In this way,
the evolution of the most important variables of the system was
analyzed during different hours of day. In Table 1, the sampling
time and its correspondent moment in the cycle are shown.
Moreover, polarization and power curves and EIS were carried
out at different times (at 13:00 h and 17:00 h along the light cycle
and at 9:00 h and 20:00 h along the dark cycle) in order to determine OCV, maximum power density and internal resistance from
polarization and power curves and ohmic and polarization resistance from impedance.
3.1.1. Daily proles of cell voltage and dissolved oxygen at the cathode
In Fig. 2a, cell voltage and dissolved oxygen at the cathode during one day are shown. During these experiments, the cathode was
operated under a 11.5 h light/12.5 h dark regime. In this way, during the light phase, algae carried out the photosynthesis absorbing
light, capturing carbon dioxide and releasing oxygen. At 9:15 h,
carbon dioxide was bubbled and, as a consequence, both dissolved
oxygen at the cathode and cell voltage fell sharply. It is suggested
that the stripping process led to lower cell voltage [15]. The plateau
was reached at 13:00 h, the cell voltage and dissolved oxygen
remained steady at approximately 18 mV and 7 mg L1, respectively, until 20:30 h, when the light was switched off and the dark
phase began. During the dark phase, algae carry out respiration and
consume oxygen. Due to this fact, dissolved oxygen decreased to
2 mg L1 and, as a consequence, cell voltage went down to
10 mV. The plateau was reached at 00:00 h and remained until
9:00 h. Schamphelaire and Verstraete studied the production of
electricity in a similar system, observing sharp uctuations in a
24 h-cycle, with a peak during daytime and minimum levels during
night [23]. Thus, it can be said that cell voltage production depends
on dissolved oxygen at the cathodic compartment, since oxygen is
the electron acceptor of the reaction according to Eq. (1). This
behavior was also observed in other publications [14,15,24,25].
Kang et al. suggested that the critical oxygen concentration is
6.6 mg L1 using a graphite cathode [26].

O2 g 2H ac 2e ! H2 Ol

The decrease in dissolved oxygen was higher than that of the

cell voltage. In this way, in Fig. 2b the drop of cell voltage versus
drop of dissolved oxygen from 20:30 h (when light was switched

Table 1
Sampling times for 24 h.
Hour

Moment of the day

8:40
9:10
10:00
16:30
20:00
20:45
21:30
23:30

Before the illumination beginning

10 min after the illumination beginning
15 min after the CO2 bubbling
Steady state during the day
The end of the illumination cycle
15 min after the dark beginning
1 h after the dark beginning
Steady state during the night

Cell voltage (mV)

3.1. Characterization of photosynthetic MFC throughout the day

20

10

18

16

14

12

10

Cell voltage
Dissolved oxygen

0
0

10

12

14

16

18

20

22

24

t (h)

(b)

18
16
14

Cell Voltage (mV)

3. Results and discussion

(a)

Dissolved oxygen (mg L-1)

an AC signal of 10% of OCV. The cathode was used as the working

electrode and the anode as the counter and the reference electrode
[22]. EIS data were tted to an equivalent circuit in order to obtain
the ohmic (or diffusion) resistance and the polarization (or charge
transfer) resistance of each electrode.

12
10
8
6
4
2
0
0

-1

Dissolved Oxygen (mg L )

Fig. 2. (a) Cell voltage and dissolved oxygen at the cathode during one day. (b) Cell
voltage versus dissolved oxygen from 20:30 h (when light is switched off) to
00:00 h.

off) to 00:00 h (when the plateau was reached) is shown. These

experimental data were adjusted to lineal equation with a correlation coefcient of 0.919, demonstrating a reasonable goodness of
t. However, it is important to highlight that the y-intercept was
no zero but 6.682 mV. It may indicate that if the dissolved oxygen
at the cathode were zero, electricity would still be on production. It
indicates that any other molecules, rather than oxygen, were acting
as electron acceptors. Some molecules added as nutrients in the
cathode (such as nitrates and sulfates) have been reported to act
as electron acceptors [9,27].
3.1.2. Evolution of other parameters for one day
Conductivity and pH at both chambers were measured at indicated hours. The conductivity is not shown because this parameter
remained constant at the cathodic compartment (around
2.4 mS cm1), and at the anodic compartment the conductivity
ranged between 500 and 600 lS cm1 all the experimental time.
In Fig. 3, pH at both compartments for 1 day can be observed.
The pH of the cathodic chamber decreased when carbon dioxide
was bubbled. This fact was expected, because carbon dioxide, once
dissolved into water, produce carbonic acid and, after that, the
equilibrium between carbonic acid, carbonate, bicarbonate is
shifted to bicarbonate/carbonate and protons are generated,
therefore, the pH of the cathodic chamber decreased down to 4.5.
After that, the pH increased up to 6 due to buffer effect of carbonic
acid/bicarbonates/carbonates and also to consumption of H+ in the
oxygen reduction reaction [24,28,29]. On the other hand, the pH at
the anodic compartment remained stable during the day, around 6.

212

A. Gonzalez del Campo et al. / Fuel 140 (2015) 209216

removal turned out to be 70% and 26%, respectively. A COD:N:P

ratio of 100:5:1 was achieved in the anodic compartment. Taking
into account the 100:20:1 COD:N:P ratio commonly required to
feed the biological reactor in a conventional urban wastewater
treatment plant [35], a minor quantity of nitrogen is necessary to
remove COD in a MFC.
In the cathodic compartment, nitrate, phosphate and sulfate
were found. These compounds were added as nutrients for algae
growth. It is important to highlight that nitrate and sulfate can
act as electron acceptor [36], according to Reaction (2) and (3),
respectively. However, any product of the reduction of these compounds was obtained. In Fig. 4b, the evolution of nitrate, phosphate
and sulfate into the cathodic compartment all day is shown. As it

pH

5
Anode
Cathode
4
8

10

12

14

16

18

20

22

24

t (h)

40

20

Fig. 3. Evolution of the pH at both compartments of the cell for one day.

38

16
14

36

12
10

6
NH+4

32

PO-3
4

-3

34

Concentration NH 4 (mg L-1)

(a)
Concentration PO (mg L-1 )

2
0
000:08

30
000:12

000:16

000:20

000:24

001:04

001:08

t (h)
400

(b)
Concentration (mg L-1)

350

300

250

200
-3

PO 4

150

NO 3
-2

SO 4

100
000:08

000:12

000:16

000:20

000:24

001:04

001:08

t (h)
30

160

-3

150

25

140
20
130
15

-2

SO 4

90
80
000:08

NO3

(mg L-1)

-3

PO 4

10

100

-2

110

120

Concentration PO (mg L-1 )

(c)

Concentration NO -SO

However, the pH at the anodic compartment was slightly declined

when carbon dioxide was bubbled at the cathodic compartment. It
was because some protons passed through the membrane from the
cathode to the anode. The pH is a very important variable in an
MFC, because microorganisms and algae can only carry out their
vital functions across a limited range of pH, from 6.5 to 8.5 for
microorganism and from 7.5 to 8 for Chlorella vulgaris [15,30,31].
Hence, it is important to maintain a neutral or slightly acid pH near
the cathode to maximize power generation [1]. In this way, the pH
of both compartments was found to be suitable for the correct
operation of photosynthetic MFC.
During this study, COD at the anodic compartment and nutrients (nitrate, sulfate, phosphate and ammonium) at both compartments were measured. COD at the anodic compartment was found
constant all day. In this way, COD removal percentage was around
75% and COD removal rate was 30.38 1.73 mg O2 h1. Thus, a
relation between cell voltage and COD removal by microorganisms
was not observed. It can be justied considering that the most of
the organic matter was consumed by non-electrogenic microorganisms, as coulombic efciency was smaller than 1%. Coulombic
efciency is a direct measure for competition between electrogens
and methanogens in a mixed culture [32]. Exoelectrogens and
methanogens share growing conditions so they compete with each
other [33]. In a broad sense, the overall organic matter consumption by anodic microorganisms was not affected by light/dark
cycles.
Microorganisms and algae require nutrients and trace elements
for optimum growth. Among them, the most important are nitrogen and phosphorous. The lack of these nutrients has an adverse
effect upon the growth and the performance of microorganisms
and algae [34]. In this way, the nutrients consumed by microorganisms (ammonium and phosphate at the anodic compartment) and
by algae (nitrate, sulfate and phosphate at the cathodic compartment) was studied. To meet the objective, ammonium, nitrate,
nitrite, sulfate, sulte and phosphate were analyzed at the efuent
of the anodic compartment and into the cathodic compartment.
Firstly, it is important to note that ammonium and phosphate
were the only compounds of nitrogen and phosphorous found at
the efuent of the anodic compartment. It indicates that nitrication process did not take place. In Fig. 4a, the evolution of ammonium and phosphates at the efuent of MFC during both cycles
light/dark (24 h period) is shown. The concentration of ammonium
and phosphate at the efuent remained steady all day, around
10 mg L1 of ammonium and 37 mg L1 of phosphate. Taking into
account ow rate and initial ammonium and phosphate concentration in wastewater, the percentage of ammonium and phosphate

18

0
000:12

000:16

000:20

000:24

001:04

001:08

t (h)
Fig. 4. Evolution of nutrients (ammonium, nitrate, sulfate and phosphates) for one
day. (a) At the efuent of the anodic compartment. (b) At the cathodic compartment. (c) In a culture of Chorella vulgaris, not connected to an MFC, during the dark
phase.

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A. Gonzalez del Campo et al. / Fuel 140 (2015) 209216

1
N2 3H2 O
2

2

SO2
8OH
4 4H2 O 8e ! S

2
3

At the beginning of the light phase, the concentration of phosphate, nitrate and sulfate decreased from 229 to 220 mg L1, 360
to 340 mg L1 and 282 to 240 mg L1, respectively. These concentrations remained constant during the light phase. When the light
was switched off, these concentrations reached a peak and soon
after, they decreased to 174, 205 and 161 mg L1, respectively.
Finally, the concentration increased before the light was switched
on. This behavior was observed on a daily basis, seven days in a
row.
To our knowledge, this behavior was unusual and had not been
reported before. In the absence of oxygen, other compounds, such
as nitrate, sulfate, iron, manganese, selenate, arsenate, urinate,
fumarate and carbon dioxide can act as terminal electron acceptors
[10,37]. Regarding their redox potentials, the cathodic potential
with nitrate, manganese, and iron as terminal electron acceptors
is comparable to oxygen [36]. On the other hand, sulfate has a
lower potential [36]. Therefore, during the dark phase, a continuous descent in the concentration of other electron acceptors (sulfate or nitrate) was expected as a result of their consumption in
the reduction reaction, due to the fact that electricity was still on
production when dissolved oxygen at the cathode was the lowest.
In the light of the electricity produced during the dark phase
(15 mV) and the stoichiometric ratios of the reduction reaction
from nitrate to nitrogen (Reaction (2)), an estimation of the theoretical consumption of nitrate (the second best electron acceptor,
right after oxygen) in the cathode can be obtained. Considering
the aforementioned assumptions, the theoretical consumption rate
1
of nitrate (from 00:00 to 08:00) was 5.78102 mg NO
, making
3 h
a total of 0.463 mg NO
in
8
h.
This
value
is
signicantly
lower
than
3
the experimental consumption measured in the cathodic compartment (80 mg NO
3 ). The same results were obtained for sulfate.
Therefore, the consumption of nitrate and sulfate because of the
reduction reaction into the cathodic compartment was negligible
and the uctuation of nutrients concentration during the dark
phase was initially put down to an indetermined process regarding
the algae.
With the aim of double-check this pattern, the evolution of
nitrate, phosphate and sulfate concentration in a culture of Chorella
vulgaris, not connected to an MFC, was studied during its dark
phase. Results are shown in Fig. 4c. As a conclusion, the same pattern was found in the new culture. In view of the results, it is clear
that any non-dened metabolic process of the algae is responsible
for the pattern observed.
On the other hand, although the initial inoculum of Chlorella
vulgaris was pure, as time goes on, other photosynthetic or hereotrophic microorganisms can appear and contaminate the culture.
However, if the last conjecture proves to be true, it did not pose
a problem to the performance of the photosynthetic MFC.
3.1.3. Electrochemical characterization during one day
In order to electrochemically characterize the photosynthetic
MFC, polarization curves and electrochemical impedance spectroscopy were carried out at 9:00 h (before the light was switched on,
dark phase), 13:00 h and 17:00 h (light phase) and 20:00 h (right
after the light was switched off, dark phase).

0,6

(a)
0,5

0,4

V (mV)

NO3 6H 5e !

[1]: Region I, a decrease of voltage due to the polarization of the

electrodes (activation losses) for low currents starting just at the
OCV; Region II, a subsequent linear decrease region (ohmic losses),
in which the resistance of the different components of the cell
limits the process; and Region III, that corresponds to the region
controlled by mass-transfer (concentration losses), in which there
is a lack of electrochemically active species arriving to the
electrodes surface. In this way, the types of losses in the MFC can
be determined considering the shape of the graph. In Fig. 5a, polarization curves at different times are shown. In the curves of the
dark phase (when oxygen concentration is low), the Region III
(concentration losses) was the predominant one. In this region,
the major losses are due to low concentration of reactants or mass
transfer [1]. In this system, it was due to low oxygen concentration
at the cathode. The slope of the Region III at 9:00 h was steeper
than at 20:00 h, this was due to the oxygen concentration was
higher at 20:00 h (after light was switched off, oxygen continued
to be consumed) than at 9:00 h (after 12 h at dark phase, oxygen
concentration was the lowest). In this way, it can be seen that
the oxygen was the most important electron acceptor at the cathode. Particularly during the dark phase, the electricity production
was heavily reliant on oxygen concentration.
At 13:00 h, the predominant region was Region III (concentration looses) as oxygen concentration was increasing. At this time,
the maximum oxygen concentration had not been reached yet.
However, at 17:00 h, the maximum oxygen concentration had
already been reached and the predominant region was Region I
(activation looses). It indicates that when oxygen concentration
was at its peak, the system was limited by the oxygen reduction

0,3

0,2

9:00 h

0,1

13:00 h
17:00 h

20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320

j (mA m-2)
50

(b)
40

13:00
30

17:00 h
20

20:00 h

10

9:00 h
0
0

3.1.3.1. Polarization curves. In an ideal polarization curve, there are

three characteristic regions of voltage decrease in a fuel cell. Each
region shows different types of losses reducing the useful current

20:00 h

0,0

P (mW m-2)

can be observed, the evolution of these compounds followed the

same pattern.

20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320

j (mA m-2)
Fig. 5. (a) Polarization curves at different times. (b) Power curves at different times.

214

A. Gonzalez del Campo et al. / Fuel 140 (2015) 209216

rate at the cathode. It was an important handicap in uncatalyzed

systems. This problem may be solved using an appropriate catalyst
in the electrode. It has been reported that oxygen has a high overpotential when uncatalyzed electrodes are used, even though it is
the most practical electron acceptor [38].
From polarization curves (Fig. 5a) and power curves (Fig. 5b),
open circuit voltage (OCV), internal resistance and maximum
power density can be calculated. In this way, in Table 2 the
obtained parameters at different times are shown.
As it can observed in Table 2, OCV, maximum power density
and internal resistance ranged during the day from 0.460 to
0.541 mV, 8.18 to 42.98 mW m2 and 8060 to 1680 O, respectively.
The highest value of maximum power density and the lowest value
of internal resistance were measured at 13:00 h, when the voltage
was in its peak and the steady state had already been reached. The
lowest value of maximum power density and the highest value of
internal resistance were obtained at 9:00 h, when output voltage
was the lowest due to the absence of oxygen. So, the low oxygen
concentration at 9:00 h caused an increase of internal resistance
and a decrease of maximum power density because the reduction
reaction was oxygen-limited. On the other hand, the highest maximum power density obtained was 42.98 mW m2 at 13:00 h. This
value was similar or higher than those obtained in other studies
using uncatalyzed MFCs [3942].
3.1.3.2. Electrochemical impedance spectroscopy. In order to determine the resistances (ohmic, or diffusion, and polarization, or
charge transfer) of each part of the cell separately, electrochemical
impedance spectroscopies were carried out at different times. The
EIS were run on the complete cell [43]. The Nyquist plot obtained
show a high polarization resistance represented by an unclosed
semicircle (representation not shown). The equivalent electrical
circuit (Fig. 6) was used to t the impedance data to obtain the
ohmic, anode and cathode polarization resistance. The equivalent
circuit model shown in Fig. 6 consists of two electrodes (anode
and cathode), each comprised of a parallel resistor and a constant
phase element (CPE), and separated by a resistor (membrane + solution resistance) [36,43].
Table 3 shows the parameters from the equivalent circuit tting
EIS data. The correlation coefcient was greater than 0.99 in all
cases except for 20:00 h measure. Firstly, the ohmic resistance
was similar all day (in light and dark phase), between 200 and
250 O, indicating that the membrane and solution resistance was

Table 2
OCV, maximum power density and internal resistance at different times.
Hour

OCV (V)

Maximum power
density (mW m2)

Internal resistance (O)

9:00
13:00
17:00
20:00

0.460
0.502
0.541
0.502

8.18
42.98
30.93
22.16

8060
1680
1840
4370

Anode
CPE a

Cathode
CPE c
Rohm

Ra

Rc
Fig. 6. Equivalent circuit.

Table 3
Parameters obtained by the adjustment of EIS to an equivalent circuit ((RQ)R(RQ)).
Hour

Ra (O)

Rohm (O)

Rc (O)

r2

9:00
13:00
17:00
20:00

1634
1776
2393
1834

204.9
250.1
198.2
200.1

12,650
6930
8810
13,210

0.996
0.991
0.995
0.976

not affected by the light or the lifecycle of the algae. This type of
resistance was the lowest in this system. The polarization resistance of the anodic compartment (Ra) was similar along the day,
as it was expected, because the photosynthetic cycle of the algae
did not affect to the anodic compartment. The Ra ranged between
1600 and 2200 O. These differences can be attributable to the
changes of the biolm as times goes on. However, the polarization
resistance of the cathodic compartment (Rc) changed during the
day as a function of the cycle of light/dark, between 6930 and
13210 O. In this way, the highest polarization resistance of the
cathodic compartment was reached at 9:00 and 20:00 h, right
when the dissolved oxygen was at its lowest, limiting or controlling the reduction reaction. On the other hand, the lowest Rc was
reached at 13:00 h when the steady state had already been
reached.
Broadly speaking, the polarization resistance of the cathodic
compartment was substantially higher than that found on the anodic one, between three- and sevenfold, approximately. This is
because of the absence of a precious catalyst in the cathode
whereas in the anode, a biolm formed on the surface of the electrode acted as biocatalyst [15,44]. In general, biocathodes have
higher electrical resistances and, therefore, higher energy losses
[10,45,46].

3.2. Life test durability

A life test consists in monitoring a variable of a process throughout a long period of time. In order to evaluate the performance of
the photosynthetic microbial fuel cell, its durability and reliability
were studied. The implementation of this system for energy supply
applications calls for a high degree of reliability. For this purpose,
some researchers have studied the durability of different elements
in a MFC for 250 days [47], six months [48] and 35 weeks of operation [49].
In this work, the life test was carried out for 10 months. This
study monitored two of the most important operational variables:
electricity production and treatment capacity. During the abovesaid period, the system was subjected to different studies, some
of them reported in previous works (study of performance of photosynthetic MFC with microorganisms in biolm and both microorganisms in biolm and suspension; study of inuence of COD
concentration in wastewater and study of different inorganic
carbon sources for algae) [50] and others shown in this work
(characterization of photosynthetic MFC throughout the day).
In this way, in Fig. 7, cell voltage (Fig. 7a), COD removal percentage (Fig. 7b) and COD removal rate (Fig. 7c) during 10 months are
shown. Blank spaces correspond to periods in which sampling or
measuring was not possible, because any other process was in progress (polarization curves, EIS, etc.).
Taking into account that cell voltage uctuated throughout the
day, in Fig. 7a the cell voltage at 5:00 h (plateau of dark phase) and
17:00 h (plateau of light phase) are plotted. The cell voltage at
17:00 h varied between 10 and 25 mV and at 5:00 h between 7
and 15 mV. The variations of this parameter are due to different
experiments carried out in the cell, which led to changing conditions in the anodic compartment. It is important to highlight that

A. Gonzalez del Campo et al. / Fuel 140 (2015) 209216

(a)

40
17:00
5:00

35

Voltage (mV)

30
25
20
15

215

wastewater (COD reduction). Moreover, the electrodes showed

no mechanical degradation with time. This is due to the presence
of Teon in its formulation, acting as a glue of the carbon paper
bers. On the other hand, although fouling of proton exchange
membrane was observed, it did not affect its performance. As the
main conclusion drawn from the durability test, it can be concluded that the system showed a great reliability, durability and
resilience under changing operational conditions.

10
5

4. Conclusions

0
0

25

50

75

100 125 150 175 200 225 250 275 300 325 350

From this work, the following conclusions can be drawn:

t (d)

Cell voltage production depended on dissolved oxygen. During

the light phase, algae produced oxygen and electricity production was at its highest. However, during the dark phase, when
dissolved oxygen was at its lowest, the electricity production
indicated that nitrates or sulfates acted as electron acceptor.
The cathodic compartment was the limiting compartment of
the system. This was because the absence of a precious catalyst
to overcome the adverse thermodynamic of the oxygen reduction reaction.
The photosynthetic MFC was stable, as far as electricity production and wastewater treatment was concerned, after 10 months
in operation.

COD removal percentage (%)

(b) 100
90
80
70
60
50
40
30
20
10
0
0

25

50

75

100 125 150 175 200 225 250 275 300 325 350

(c)

60

COD removal rate (mg h-1)

t (d)

50

Acknowledgement
Authors thanks the JCCM for the nancial support thorough the
Project POII10-0329-5194.

40

References

30
20
10
0
0

25

50

75

100 125 150 175 200 225 250 275 300 325 350

t (d)
Fig. 7. (a) Cell voltage at 5:00 h and 17:00 h. (b) COD removal percentage. (c) COD
removal rate for 10 months.

the range of variation was wider in the plateau of the light phase
than in the plateau of the dark. It is because during the dark phase,
the cathode was the limiting compartment and, therefore, the production of electricity was determined by the performance of this
compartment irrespective of the conditions in the anodic one.
In Fig. 7b, COD removal percentage versus operation time is
shown. This parameter ranged between 40% and 90%. Finally, the
COD removal rate versus time can be observed in Fig. 7c, it varied
between 15 and 40 mg O2 h1. The variations of these variables
were due to the change of operation conditions in different
experiments.
Considering the aforementioned results (cell voltage, COD percentage and removal rate), it can be stated that the photosynthetic
microbial fuel cell was effectively abating COD and producing
electricity during 10 months with no dead times (avoiding reinoculations or any other operational problems). Concerning electricity production, the system has demonstrated to be robust and
stable, with the additional advantage of effectively treating the

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