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Sustainable desalination using a microbial capacitive desalination cell
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Transcript of Sustainable desalination using a microbial capacitive desalination cell
Dynamic Article LinksC<Energy &Environmental Science
Cite this: Energy Environ. Sci., 2012, 5, 7161
www.rsc.org/ees PAPER
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Sustainable desalination using a microbial capacitive desalination cell†
Casey Forrestal,a Pei Xub and Zhiyong Ren*a
Received 15th January 2012, Accepted 13th March 2012
DOI: 10.1039/c2ee21121a
Microbial desalination cells (MDCs) use the electrical current generated by microbes to simultaneously
treat wastewater, desalinate water, and produce bioenergy. However, current MDC systems transfer
salts to the treated wastewater and affect wastewater’s beneficial use. A microbial capacitive
desalination cell (MCDC) was developed to address the salt migration and pH fluctuation problems
facing current MDCs and improve the efficiency of capacitive deionization. The anode and cathode
chambers of the MCDC were separated from the middle desalination chamber by two specially
designed membrane assemblies, which consisted of cation exchange membranes and layers of activated
carbon cloth (ACC). Taking advantage of the potential generated across the microbial anode and the
air-cathode, the MCDC was capable of removing 72.7 mg total dissolved solids (TDS) per gram of
ACC without using any external energy. The MCDC desalination efficiency was 7 to 25 times higher
than traditional capacitive deionization processes. Compared to MDC systems, where the volume of
concentrate can be substantial, all of the removed ions in the MCDC were adsorbed in the ACC
assembly double layer capacitors without migrating to the anolyte or catholyte, and the electrically
adsorbed ions could be recovered during assembly regeneration. The two cation exchange membrane
based assemblies allowed the free transfer of protons across the system and thus prevented significant
pH changes observed in traditional MDCs.
Introduction
The increasing awareness of the water-energy nexus is compelling
the development of technologies that reduce energy requirements
during water treatment as well as water demands for energy
production.1,2 Microbial desalination cells (MDCs) recently
aDepartment of Civil Engineering, University of Colorado Denver, Denver,CO 80004, USA. E-mail: [email protected]; Tel: +1 (303)556-5287bCivil and Environmental Engineering, Colorado School of Mines, Golden,CO 80401, USA
† Electronic supplementary information (ESI) available: Two additionalfigures are included. See DOI: 10.1039/c2ee21121a
Broader context
Traditional desalination technologies are energy intensive and gen
desalination cell (MCDC) developed in this study presents an adv
removal and management without using any external energy. The M
with microbial desalination cells (MDCs) including salt migration a
assemblies for capacitive adsorption of ions, the MCDC increases d
(CDI). It is also the first reactor to remove ions from the anode, c
capability in simultaneous salt management, wastewater treatment,
MCDC regeneration also makes salt production possible. The p
directions to the development of sustainable water and energy syst
This journal is ª The Royal Society of Chemistry 2012
emerged as a promising technology to simultaneously treat
wastewater, desalinate saline water, and produce renewable
energy such as electricity or hydrogen gas.3–10 MDCs share the
same principle of bioelectrochemical reactions with microbial
fuel cells (MFCs): electrochemically active bacteria in the anode
chamber oxidize biodegradable substrates and generate electron
flow (i.e. current) to reduce the electron acceptors in the cathode
chamber. The additional desalination function can be achieved in
an MDC by adding a middle chamber containing saline water
and utilizing the anode–cathode potential difference to drive the
migration of anions (e.g., Cl�) to the anode chamber and cations
(e.g., Na+) to the cathode chamber for charge neutrality.3 The
MDC process carries great potential in desalination systems,
erate large amounts of concentrate. The microbial capacitive
anced bioelectrochemical approach to achieve sustainable salt
CDC systematically addressed challenges currently associated
nd pH fluctuation problems. Using high surface area electrode
esalination efficiency by 7–25 times over capacitive deionization
athode, and desalination chamber, which enhances the reactor
and energy production. The nearly full recovery of salt during
roof-of-concept MCDC provides valuable insights and new
ems to address the water-energy nexus.
Energy Environ. Sci., 2012, 5, 7161–7167 | 7161
Fig. 1 Diagram of MCDC reactor configuration and operation. Two
CEM-ACC assemblies were used to separate the three chambers and
capture the removed salts, as well as allow the free transfer of protons.
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because it can either be used as a stand-alone process or serve as
a pretreatment for conventional desalination processes such as
reverse osmosis (RO) to reduce the salt concentration of RO feed
and minimize energy consumption and the membrane fouling
potential. Current desalination technologies, such as RO and
electrodialysis (ED), are energy and capital intensive. Even the
most advanced large scale seawater RO units require 3–7 kW h
m�3 for water desalination, while conventional multi-stage flash
evaporation requires 68 kW h m�3.11 In contrast, the MDC
system is considered to be an energy gaining process because it
converts the biochemical energy stored in wastewater to elec-
tricity or hydrogen gas. Lab scale MDC studies showed that 180–
231%more energy can be recovered as H2 than the reactor energy
input when desalinating 5–20 g L�1 NaCl solutions,4,6 and
a recent study calculated that a litre-scale MDC can produce up
to 58% of the electrical energy required by downstream RO
systems.8
Current MDC systems use an anion exchange membrane
(AEM) to separate the anode and middle chamber, and a cation
exchange membrane (CEM) to separate the cathode and middle
chamber. Similar to electrodialysis, desalination in MDC is
achieved by direct transport of salts from the middle chamber to
the anode and cathode chamber. This system faces two main
problems. While salts get removed from the middle chamber,
they become concentrated in the anode and cathode chambers,
resulting in an increase of the volume of saline water. This
concern becomes more imperative when wastewater is treated as
the anolyte. Although the addition of ions (or total dissolved
solids, TDS) increases wastewater conductivity and benefits
electricity generation, the increased salinity may affect effluent
water quality and prevent subsequent beneficial use of treated
wastewater.12,13 The high salinity may also affect wastewater
treatment efficiency in MDCs because studies showed that high
chloride concentration is inhibitory to biological treatment,
especially for nutrient removal.14 In addition, the AEM between
the anode and middle chamber inhibits the free transfer of H+
accumulated in the anolyte to other chambers, which causes
a significant pH drop in the anode chamber and pH increase in
the cathode chamber.15,16 A previous study showed that the pH
of the wastewater anolyte dropped to 4.2 in one batch cycle if no
buffer was added to the anolyte.6 Additionally, the catholyte pH
could increase to 11–13 due to the loss of H+.6,16 This pH fluc-
tuation significantly inhibits bioelectrochemical reaction effi-
ciency and reduces system performance.
In order to modulate the movement of salts to the anode and
cathode chambers, the concept of capacitive deionization
(CDI)17 was incorporated in this study to develop a sustainable
desalination system called a microbial capacitive desalination cell
(MCDC). In the proof-of-concept MCDC, salt water can be
deionized through electrochemical ion adsorption driven by the
electrical field generated by microorganisms. Two activated
carbon cloth (ACC) membrane assemblies were designed to
connect with the anode and cathode and adsorb ions from water.
During desalination, the ions are stored in the electrical double
layer capacitors between the solution and the ACC assembly
interfaces, thus preventing the salinity increase in treated
wastewater. After the ACC is saturated with adsorbed ions, the
assembly can be regenerated by removing the electrical potential
and the retained salts can be fully recovered in situ for disposal or
7162 | Energy Environ. Sci., 2012, 5, 7161–7167
further salt recovery. Another innovative aspect of the MCDC,
as compared to conventional MDC, is the use of a second CEM
in lieu of AEM between the anode and desalination chamber
(Fig. 1). This configuration allows cations and protons to move
freely from the anode chamber throughout the reactor and
therefore maintains electrochemical neutrality and prevents pH
fluctuation. In this study, the proof-of-concept MCDC devel-
opment and operation are demonstrated, and its advantages over
current systems and application potentials are discussed.
Materials and methods
MCDC reactor design
The MCDC reactors consisted of three polycarbonate cube-
shaped blocks with 3 cm diameter holes forming an internal
anode, cathode, and desalination chamber volume of 23 mL,
27 mL, and 10 mL respectively. The anode and cathode cham-
bers had a length of 4 cm, while the desalination chamber had
a length of 1.5 cm. The anode electrode was a graphite brush
(Golden Brush, CA) and was pretreated by washing in acetone
and heating to 350 �C for 30 minutes.18 Traditional air-cathodes
were made by applying 10% Pt/C (0.5 mg cm�2) and four PTFE
diffusion layers on 30% wet-proofed carbon cloth as previously
described.19 The desalination chamber was separated from the
anode and cathode chamber by two assemblies. Each assembly
was constructed by placing a cation exchange membrane (CMX-
SB, Astom Corporation, Japan), a Ni/Cu mesh current collector
(McMaster Carr, IL), and 3 layers of Zorflex� activated carbon
cloth (ACC, Chemviron Carbon, UK) together. Additionally,
the CEM faced the anode/cathode chamber to prevent microbial
growth on the assembly. The total weight of the ACC was 1 gram
with the specific surface area of 1019.8 m2 g�1, determined by the
Brunauer–Emmet–Teller (BET) method (ASAP 2020, Micro-
meritics, Norcross, GA).20 The ACC assemblies were connected
to the anode/cathode by titanium wires (Fig. 1).
MCDC operating conditions
Two reactors were inoculated with anaerobic sludge from the
Englewood-Littleton Wastewater Treatment Plant (Englewood,
CO) and operated in fed-batch MFC mode. When a repeatable
This journal is ª The Royal Society of Chemistry 2012
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voltage profile was obtained for consecutive batch cycles, the
reactors were shifted to fed-batch MCDC mode by inserting
a pair of assemblies and adding one middle chamber as described
previously. The anolyte growth media contained per litre: 1.6 g
NaCH3COO, 0.62 g NH4Cl, 4.9 g NaH2PO4$H2O, 9.2 g
Na2HPO4, 0.26 g KCl, and 10 mL trace metals and 10 mL
vitamin solution.21 The catholyte contained per litre: 10 g KCl,
0.68 g KH2PO4, 0.87 g K2HPO4. Potassium chloride was used in
the cathode chamber to differentiate with sodium transport and
monitor the movement of cations from the cathode to the
desalination chamber. The salt solution in the desalination
chamber contained per litre: 10 g NaCl, 0.49 g NaH2PO4$H2O,
0.92 g Na2HPO4. A small amount of buffer was added to the salt
solution to some extent mimic the 300 to 700 mmol kg�1 natural
buffering capacity of seawater and prevent potential scaling at
high pH values.22
Two experimental procedures and two controls were per-
formed to investigate the desalination performance of the
MCDC system. The first experiment investigated simultaneous
physical and electrical adsorption capacity by directly adding salt
solution into the desalination chamber equipped with ACC
assemblies free of adsorbed ion. When the anode and cathode
electrodes were connected to the ACC assemblies, physical and
electrical adsorption on the ACC assemblies could occur
concurrently. The second experimental procedure investigated
only electrical adsorption capacity. Electrical adsorption
capacity of the ACC assemblies was determined by first adding
salt solution to the desalination chamber to allow complete
physical adsorption. Electrical adsorption was then characterized
by replacing the desalted solution with fresh solution, and con-
necting the two assemblies to the anode and cathode, respec-
tively. Any residual water from previous experimental washing
would have been removed when the salt solution was replaced.
Abiotic control experiments were performed by using new
brush anodes without bacterial acclimation. The first control
experiment measured the physical adsorption capacity by short
circuiting the assemblies to ensure no charge was formed across
the electrodes. The adsorption capacity of the assemblies was
defined as the change in initial and final salt concentration. The
second control investigated the electrical adsorption capacity by
first allowing complete physical adsorption to occur then by
connecting the assemblies to an external power supply at
a voltage of 0.53 V to simulate the voltage generated by
a microbial fuel cell. TheMDC control experiment used an anion
exchange membrane next to the anode chamber (Astom
Corporation, Japan) and a CEM next to the cathode chamber
without ACC assemblies in the desalination chamber. An
external resistor of 1000 Ohms was used between the anode and
cathode electrodes, and all other experimental procedures were
identical to the MCDC experiments.
To regenerate the ACC assemblies in situ for all experiments,
the assemblies were either allowed to naturally regenerate or
were regenerated by applying an external voltage to increase the
rate of regeneration. The natural regeneration was performed by
disconnecting the anode and cathode from the assemblies and
creating a short circuit between the assemblies with an external
wire. Alternatively, an external voltage of 1 V in reverse polarity
was applied to the assemblies by a programmable power source.
The external voltage was applied for 5–10 minutes and followed
This journal is ª The Royal Society of Chemistry 2012
by short circuiting the ACC assemblies, as mentioned above, for
20–30 minutes. When the potential difference reached �0.5 mV,
the ACCs were assumed to be regenerated, meaning that any
electrically adsorbed ions should have been removed from the
electrodes. After regeneration, all electrolytes were emptied and
washed with deionized (DI) water to remove any residual salt
remaining in the chambers before starting a new batch cycle.
Analysis and calculations
Conductivity and pH were measured for all three chambers using
a conductivity meter and pH meter (HACH Co., CO). The
change in the reactor’s internal resistance was determined
through electrochemical impedance spectroscopy (EIS) tests
using a Potentiostat. EIS measurements were performed by using
the anode as the working electrode, the cathode as the counter
electrode, and a saturated Ag/AgCl reference electrode placed in
the anode chamber. Results were fitted into equivalent circuit
models developed in our previous EIS studies and plotted using
Nyquist plots where the ohmic resistance is defined as the
intercept of the Zreal axis.21 Samples of all three chambers were
collected before and after desalination, and after regeneration.
Ion concentrations were measured using the Optima 3000
Inductive Coupled Plasma (ICP) Spectrometer (Perkin Elmer,
CT) and Dionex DC80 ion chromatography system (IC) (Dio-
nex, CA). Using the data from the IC and ICP, the mass balance
of the major ions was determined by summing the concentrations
of the ions in each chamber initially, after desalination, and after
recovery of the salts. Internal power used was calculated using
the following equations:
P ¼ðV 2
Rdt (1)
R ¼ rL
A(2)
where P is power in terms of watt hours, V is the voltage, R is the
resistance, r is resistivity, L is length of the resistance, and A is
the cross-sectional area. Comparisons between the MCDC and
CDI were made based off either presented data or estimations
from figures in published papers. Comparison to membrane
capacitive deionization (MCDI) was not conducted due to the
incompatibility in methodology to the MCDC.
Results and discussion
Reactor desalination performance
During MCDC operation, an electrical potential was generated
across the microbial anode and air-cathode and applied to the
two ACC assemblies to form a double layer capacitor23–30
(Fig. 1). The formation of the double layer capacitor has been
fully modeled using the Gouy Chapman–Stern theory.29 The
potential drives the ions to move from the salt solution and
adsorb on the activated carbon cloths. The ion adsorption can be
observed proportional to the charge formed between the ACC
assemblies (Fig. 2). Fig. 2 shows that, in repeated batch cycles,
when the potential on the assemblies increases from 0 to more
than 530 mV in each cycle, the solution conductivity in the
desalination chamber decreased by 12–18%, from 18 mS cm�1 to
Energy Environ. Sci., 2012, 5, 7161–7167 | 7163
Fig. 2 The correlation between the charge potential across the ACC
assemblies and the conductivity changes in the desalination chamber due
to electrical adsorption. Arrows indicate changes in electrolyte solution in
batch cycles.
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below 16 mS cm�1. The desalination rate was the greatest at the
beginning of each cycle and then decreased gradually, suggesting
the adsorption capacity of the ACC assemblies decreased along
with the increased amount of salt that had been adsorbed in the
assemblies. Salt removal was characterized by both conductivity,
measured using a conductivity meter, and total dissolved solids
(TDS) concentration, measured by IC and ICP (Table 1).
Through simultaneous physical and electrical adsorption, the
MCDC removed 26.9% of the conductivity or 25.5% of TDS
from the desalination chamber in one batch cycle. In addition,
a small percentage of salt was removed from the anolyte (4.4%)
and catholyte (10.4%) as well. This is likely due to the ions that
were driven across the membranes by the electrical potential of
the ACC assemblies from the anode and cathode chamber and
then adsorbed onto the ACC. Further experiments showed that
electrical adsorption alone removed 22.3% TDS from the desa-
lination chamber, which contributed up to 88% of the TDS
removal compared to the combined physical and electrical
adsorption experiments.
Table 2 compares the normalized TDS removal between the
MCDC and CDI studies. The results showed that for the same
amount of adsorptive material (ACC), the MCDC improved
TDS adsorption by 7–25 times. Both MCDC and CDI use an
electric field between two electrodes that electrochemically
adsorb ions, but the high adsorption from the MCDC may be
attributed to the unique feature of the MCDC that uses the
internal potential generated by microorganisms. This in situ
Table 1 Salt removal in terms of conductivity and total dissolved solids in t
Physical/electrical adsorption
Desalinationchamber
Anodechamber
% Removal in conductivity 26.9 � 5.1 13.1 � 3.8% Removal in TDS 25.2 � 3.6 4.4 � 3.6Total TDS adsorption(mg TDS per g ACC)
7164 | Energy Environ. Sci., 2012, 5, 7161–7167
approach avoided the use of an external power supply and circuit
and reduced transportation energy loss, so it demonstrated
higher efficiency than traditional CDI processes. The salt
adsorption rate inMCDC, however, is lower than published CDI
studies, and that is mainly due to the low kinetics of the fed-batch
operation and the limited amount of ACC available for ion
adsorption. In this study, theMCDC configuration was modified
from traditional cubic type MDCs, which only allowed for
a total of 1 g activated carbon cloth being used in the assembly.
This may explain why the amount of salt removed in the desa-
lination chamber was relatively small. It was calculated that the
amount of salt added in the desalination chamber (114 mg TDS)
was drastically beyond the control electrical adsorption capacity
of the ACC (8.5 mg TDS for the 1 g ACC applied). Moreover,
compared to CDI systems that consume 0.21–1.78 Watt hour
external energy to generate the potential to remove 1 g TDS, the
MCDC system does not use any external energy but instead
utilized the in situ potential difference between the ACC assem-
blies generated during microbial activities. It was calculated that
the MCDC reactor saved 2.18 Watt hour for 1 g of TDS
removed. That is why in Table 2 the net energy used for the
MCDC is negative, indicating that 2.18 W h g�1 TDS removed
was not required, while for the CDI systems an external energy of
0.2–1.78 W h is required for removal of 1 g TDS. While the
MCDC reactor directly uses generated current for desalination,
it is possible for electricity to be generated by applying an
external load across the ACC assemblies during regeneration.
Reactor configuration optimization is underway to increase the
ACC loading and further improve desalination efficiency.
Sodium, chloride, potassium, and phosphate accounted for
greater than 85% of the TDS, and their specific concentration
changes in the three chambers are shown in Fig. 3. In addition to
direct capacitive electrical adsorption that caused concentration
decreases in the desalination chamber, a small amount of charged
ions migrated from the anode and cathode chamber to the
desalination chamber due to the electrical potential or concen-
tration gradient. However, the desalination efficiency for the
anode and cathode chambers is low compared to the salt removal
in the desalination chamber due to the lack of electrical double
layer adsorption and the inhibited anion transfer across cation
exchange membranes. Results in Table 1 showed that saline
water can also be used as the catholyte and partially desalinated.
Further desalination can be achieved by feeding the treated
catholyte to the subsequent reactor’s desalination chamber.
The reactor’s internal resistance as measured by EIS at the
beginning of the desalination cycle was on average 8.5 Ohms.
After desalination, the internal resistance increased to an average
he MCDC
Electrical adsorption
Cathodechamber
Desalinationchamber
Anodechamber
Cathodechamber
5.6 � 4.4 10.0 � 0.2 10.6 � 3.5 �2.0 � 2.710.4 � 3.6 22.3 � 3.6 7.6 � 3.6 2 � 3.672.7 50.7
This journal is ª The Royal Society of Chemistry 2012
Table 2 Desalination efficiencies in the MCDC and CDI reactorsa
Method Electrode materialsElectrodedistance (mm)
Net W h/g TDSremoved
mg TDS/g adsorptivematerial Reference #
MCDC Activated carbon cloth 15 �2.18 50.74 This paperCDI Carbon aerogel 2.3 +0.21 7.00 17CDI Activated carbon powder NA +1 1.95 24CDI Activated carbon powder 0.1 +1.78 2.88 25CDI Activated carbon powder 0.1 +1.68 3.11 26CDI Activated carbon powder with
mesoporous carbon black0.22 NA 3.82 27
CDI MnO2/nanoporous carbon composite NA NA 0.10 28CDI Activated carbon cloth NA +0.52 NA 30CDI Activated carbon cloth with titania NA NA 4.38 34
a NA ¼ not available.
Fig. 3 The concentration changes of the four major ions (potassium,
sodium, chloride, phosphate) before and after one typical batch cycle of
MCDC operation. Fig. 4 Mass balance of the four major ions (potassium, sodium, chlo-
ride, phosphate) in the MCDC reactor before and after regeneration.Dow
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of 13 Ohms (ESI†). The change in conductivity in the desalination
chamber correlated closely with the change in internal resistance
for the reactor over the course of desalination. The MCDC
reactor’s ability to transfer electrons was not inhibited as occurs
over the course of desalination in standard MDCs. It is theorized
that this is due to the MCDC’s ability to maintain charge
neutrality better than MDC reactors. In standardMDC reactors,
charge neutrality is reached by ion migrating out of the desali-
nation chamber, while in the MCDC reactor charge neutrality is
performed by ion migrating through the entire reactor.
Assembly regeneration and salt recovery
The ion saturated ACC assemblies were regenerated using two
approaches. The natural regeneration was accomplished by
directly connecting the two assemblies in short circuit. The
electrical potential across the assemblies was dissipated with
the adsorbed salts being released back into solution. When the
potential difference across the ACC assemblies reached
�0.5 mV, it was assumed that the ACC assemblies were regen-
erated with complete electrical salt desorption. The regeneration
rate can be significantly increased by connecting the assemblies
to an external power supply of 1 V with reverse polarity to
facilitate ion desorption (ESI†). Fig. 4 shows that among the four
major ion species, almost all of the electrical adsorbed salts were
This journal is ª The Royal Society of Chemistry 2012
recovered during assembly regeneration, shown as a direct
correlation between the initial and recovered salt concentrations.
The capability of in situ regeneration of the ACC assemblies is
another advantage of the MCDC, because the assemblies can be
reused many times without investing significantly in materials.
Almost all of the adsorbed salts can be recovered in concentrates
during regeneration, and the recovered salts can be dewatered or
extracted for beneficial uses. Furthermore, MCDC stacks can be
developed and integrated with reverse electrodialysis (RED) to
capture the energy generated due to the salinity gradient across
the concentrate and freshwater.31,32 The current MCDC is
operated in batch mode, and the desalination and regenerated
processes were conducted sequentially. More efficient operation
can be achieved by connecting multiple reactors in series or in
parallel and operating them in complementary sequential batch
reactor (SBR) modes. While some of the units perform desali-
nation, others conduct assembly regeneration at the same time.
This operation not only provides a continuous flow of produced
freshwater but also allows for the direct usage of the electricity
produced from regeneration units for desalination units.
Reduced pH fluctuation
Fig. 5 shows the change in pH units among the three chambers
over one typical batch cycle for both the MCDC and the control
Energy Environ. Sci., 2012, 5, 7161–7167 | 7165
Fig. 5 The change in pH for the MCDC anode, cathode, and desali-
nation chambers compared to the control MDC in one batch cycle. The
initial pH values in the chambers of MDC orMCDC all ranged 7.0� 0.2.
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MDC. The initial pH values in the chambers were all within 7.0�0.2. The change in pH for the anode chamber in both the MCDC
and the MDC was relatively small, with a drop in pH of between
0.2 and 0.5 pH units, which was presumably attributed to the
high buffering capacity of the anolyte. However, the catholyte
had drastically different results between the MCDC and MDC,
with the MCDC increasing in pH on average 1.5 pH units and
the MDC increasing 4.4 pH units. Interestingly the change in pH
for the desalination chamber for the MCDC is greater than for
the MDC control. Previous capacitive deionization studies
showed that water electrolysis may cause slight pH variation at
low voltages, which may explain the pH increase in the MCDC
desalination chamber.30 It is difficult to compare the MCDC
results directly with CDI studies, because no known CDI
experiments have been conducted at a set potential lower than
0.6 V.23–30 Further investigations should explore the cause of this
phenomenon.
Because the average percent change between the cathode and
desalination chamber were essentially the same, it is assumed
that the proton transfer capability of the reactor was not
inhibited. TheMCDC employs a CEM to separate the anode and
desalination chamber. This is different from the AEM used in
current MDCs and releases the pH fluctuations in the reactor. In
traditional MDCs, anions (Cl�) migrate from the desalination
chamber to the anode chamber to compensate for the accumu-
lation of H+, but because the AEM prevents the transfer of H+
out of the anode chamber, a decrease in pH is observed. By using
a CEM, the accumulated H+ not only can transfer to the desa-
lination chamber but also can transfer further to the cathode
chamber and therefore solves the pH change problem in the
entire MCDC reactor. Previous studies show that other ions such
as Na+ and K+ also play important roles in maintaining charge
balances across different chambers in microbial fuel cells,33 but
the majority of such ions are adsorbed in the ACC assemblies, so
electrolyte charge balance due to ion transfer is not a concern in
the MCDC.
Outlook
The integration of capacitive deionization with microbial desa-
lination provides a sustainable solution that not only addresses
7166 | Energy Environ. Sci., 2012, 5, 7161–7167
the salt migration and pH fluctuation problems facing current
MDC systems, but also improves salt removal and energy effi-
ciency compared to CDI systems. Traditional MDCs remove
salts from the desalination chamber, but they also add TDS to
the anode and cathode chambers and may increase the volume of
saline water significantly, depending on different operation
configurations.3–10 The MCDC reactor demonstrated that desa-
lination can be accomplished in the middle chamber without
adding salts to the anolyte and catholyte, and therefore released
the concerns on the viability of wastewater treatment and reuse
due to increased TDS concentration. This proof-of-concept
system also demonstrates a microbial desalination reactor to
reduce salinity in all three chambers of the reactor. The MCDC
system offers a sustainable desalination, renewable energy
production, and wastewater treatment. To maximize the benefits
and prevent negative effects of salinity changes on the waste-
water anolyte, salt migration from the desalination chamber
could be modulated by constructing modular plate-shaped ACC-
membrane assemblies. If added salt is desired in wastewater to
improve the anolyte conductivity, regular MDC operation could
be performed. If salt should be prevented frommigrating into the
anode chamber, the modular ACC assembly plate can be inserted
into the reactor to perform salt adsorption. This system inte-
gration and operation will provide microbial desalination
systems with great flexibility in salt migration management as
well as better pH fluctuation control.
Despite the potential benefits offered by the MCDC system,
many challenges remain to be addressed based on the informa-
tion collected from this proof-of-concept study. In addition to
the low-cost material development that is required for all bio-
electrochemical systems, the adsorptive material can be
improved, such as with silica or titanium modification.34,35 The
reactor configuration needs to be optimized to provide more
ACC loading and improve diffusion rate and adsorption capa-
bility. Modular stack reactors and flexible operation strategies
need to be developed to maximize the integration of desalination
and assembly regeneration in multiple units, optimize water
recovery, and enhance salt migration management. Improve-
ments in MCDCs will also benefit from the continued advances
of other bioelectrochemical systems such as microbial fuel cells
and capacitive deionization, with the eventual goal of developing
a full scale sustainable system directed toward the integration of
multiple functions, such as extracting energy from wastewater
and water desalination.
Acknowledgements
This work was supported by the Office of Naval Research (ONR)
under Awards N0001410M0232. We thank Dr Peter Jenkins for
his suggestions and reviewers for their helpful comments.
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