Renewable and Sustainable Energy Reviews 76 (2017) 1022–1031

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Third generation in bio-electrochemical system research – A systematic MARK

review on mechanisms for recovery of valuable by-products from
wastewater
⁎,1
Dipak A. Jadhava,1, Sreemoyee Ghosh Rayb,1, Makarand M. Ghangrekarc,
a
School of Water Resources, Indian Institute of Technology, Kharagpur 721302, India
b
P. K. Sinha Center for Bioenergy‚ Advanced Technology Development Centre, Indian Institute of Technology, Kharagpur 721302, India
c
Department of Civil Engineering, Indian Institute of Technology, Kharagpur 721302, India

A R T I C L E I N F O A BS T RAC T

Keywords: Bio−electrochemical system (BES) mainly focused on bio−energy generation in the form of methane and
Bio-electrochemical system bio−hydrogen while treating wastewater in anodic chamber. The potential of BES to produce intermittent
By-products recovery chemicals and high-value derivatives has been immensely explored since last decade by adopting modified
Heavy metals recovery reaction kinetics. This review article deals with the mechanism of recovery of resources and by-products during
Microbial fuel cells
redox reactions in BES. The BES offers flexible platform for both oxidation and reduction processes.
Redox reactions
Development of BES for product synthesis via bio-electrochemical pathway has greatly extended the new
Wastewater treatment
horizon in bioenergy research. Microbial fuel cell and microbial electrolysis cell, the major two variants of BES,
are useful to convert the energy present in wastewater to recover resources like bio-electricity, hydrogen,
nutrients, heavy metals, minerals and industrial chemicals. Thus, after improving the performance of BES,
widening the scope for products recovery by developing better understanding of the process and with efforts to
reduce its production cost, it can become a sustainable technology for treatment of wastewater with added
advantage of recovery of resources and bio-energy generation.

1. Introduction system (BES) can exploit the process of electrochemical conversion of

1.1. Energy status and importance of by-product recovery
The national energy policy drivers of any country are the energy
security, energy growth and environmental protection. Being an
indispensable part of human life, energy and water necessitate
environmental protection. Increasing population and high rate of
economic growth proportionately increases the environmental pollu-
tion as well. In developing countries pollution is exceeding with rapid
industrialization and urbanization, leading to generation of enormous
amount of solid waste and wastewaters; hence, a few technological
suggestions are arising regarding its proper utilization as a potential
source of energy and exploiting by-products recovery. Considering
wastewater solely as a source, the energy potential contains in it could
be five times more than the energy consumed to treat it [1].
The ecological impact associated with global energy crisis demands
to recover the useful forms of energy by adopting more recent
technologies. A rapidly developing technology of bio−electrochemical
organic matter to generate usable by-products, fuels and bio-electricity
by microbial metabolic conversion [2]. BES offers a set of configura-
tions that can convert chemical energy present in waste (oxidizable
organic matter) into electricity or other valuable products. Studies on
BES have been majorly focused on its high efficiency of energy
conversion, microbes-anode interaction and up-scaling. Some specific
application niches of bio-electrochemical technology (BET) over com-
mercially applicable conventional anaerobic digestion (AD) processes
are, (i) the ability of treating organic substrates even at lower chemical
oxygen demand (COD) concentration in the wastewater and also at
higher concentration of volatile fatty acids (VFAs), (ii) feasibility of
operation at lower operating temperature (20 °C), (iii) reduced sludge
production, hence possible reduction of operating cost associated with
sludge handling and disposal, and (iv) reduced cost for aeration. Thus,
a promising and sustainable technical solution can be provided by
employing two major variants of BES: microbial fuel cell (MFC) and
microbial electrolysis cell (MEC) for recovery of renewable energy with
high yield and useful chemical by-products [3]. According to the mode

⁎
Corresponding author.
E-mail addresses: deepak.jadhav1795@gmail.com (D.A. Jadhav), gr.sreemoyee@gmail.com (S. Ghosh Ray), ghangrekar@civil.iitkgp.ernet.in (M.M. Ghangrekar).
1
All authors contributed equally.

http://dx.doi.org/10.1016/j.rser.2017.03.096
Received 26 January 2016; Received in revised form 22 January 2017; Accepted 21 March 2017
1364-0321/ © 2017 Elsevier Ltd. All rights reserved.
D.A. Jadhav et al.
of application of BES, another two up-coming research approaches
such as, enzymatic fuel cell (EFC) and microbial solar cell (MSC) are
being developed and are getting popular [4].
To address to the issues of energy and water crisis, the novel
approach of MFC can be exploited to treat wastewater along with
simultaneous electricity generation using microbes as biocatalyst. Most
of the MFC research has been focused on wastewater treatment and
electricity generation. However, MFC can also offer a promising option
for by-products recovery (heavy metals and redox chemicals) from
wastewater [5,6], which needs to be explored more. In MEC system,
due to the application of controlled external voltage to cathode, the
reaction between proton and electron can lead to formation of
hydrogen, methane, hydrogen peroxide and other high-value end
products, having further potential to expand the MEC applications.
Enzymatic fuel cell with immobilized enzymes on electrodes imposes
higher catalytic oxidation of substrate. Specific enzymatic reaction
imparts utilization of redox mediators, demonstrating better electron
transfer efficiency in such fuel cell [7,8]. The aim of this article is to
review the scope of different valuable by-products recovery through
redox mechanisms, while treating wastewater in BES. A detailed
description on recovery of few important but less discussed chemical
by-products and the mode of their simultaneous production in BES has
also been discussed in this paper. The processes are mainly focussed to
discuss the mode of chemical synthesis during biological conversion,
fundamental and theoretical outlook of process parameters and value-
addition by chemical recovery, which provide a significant knowledge
contribution with effective solution to formulate more efficient waste-
water treatment processes. Application niches, limitations and possible
reactor modifications are also suggested to achieve higher yield of by-
products and bio-energy generation.
1.2. Principle of BES
Application of BES is a novel approach based on electrochemical
conversion processes, capable of converting the chemical energy stored
in biodegradable organic materials by catalytic activity of microorgan-
isms. BES consists of anodic (oxidative) and cathodic (reductive) half-
cells to produce electricity or other chemically derived products (Fig. 1)
by integrating the biochemical and electrochemical processes.
Electrochemically active bacteria (EAB) catalyse the oxidation of
organic electron donors in the anodic chamber and deliver electrons
to the anode, which can be captured directly as bio-electricity. To
maintain the electro-neutrality, protons (H+) generated during the
catalytic conversion travels through cation exchange membrane from
anodic chamber to cathodic chamber, where protons are utilized to
Fig. 1. Schematic diagram of bio-electrochemical system.
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Renewable and Sustainable Energy Reviews 76 (2017) 1022–1031
produce value-added chemicals under imposed external potential. In
the last two decades, BES has drawn significant attention of the
researchers due to its promising applications in scientific fields such
as renewable energy production, bioremediation, wastewater treatment
[9] and other by-product recovery. In this direction, considerable
amount of literature exists, suggesting its basic operations, architec-
ture, applications [10,11], scale-up requirements [12], mode of elec-
tron transfer by anode-respiring bacteria [13,14] and their metabolism,
energy losses [15,16], cathodic limitations [17,18] and critical compar-
ison between BES and conventional anaerobic technologies [3,10,19].
Also, BET offers a new and transformative solution for integrated
wastewater treatment processes leading to recovery of energy and
resources, which provides a flexible platform for both oxidation of
pollutants and reduction oriented methods for product recovery [20].
1.3. Advancement in BES research
In early 1911, Potter [21] discovered bacterial capability to oxidize
the organic matter using an electron accepting anode. During first
generation, the BES research was mainly focused on organic matter
removal during wastewater treatment. Combination of hybrid ap-
proach of wastewater treatment processes using BES helped to enhance
the treatment of wastewater. With advancement in multidisciplinary
research, this technology was used to recover energy in the form of
electricity, hydrogen and intermediate products, during second gen-
eration of BES research. One order of magnitude increment in power
density from MFC was achieved with the help of modified electrode
materials, application of novel catalysts, improved understanding of
mechanisms and microbial electrogenic pathways for substrate oxida-
tion and modifications in geometry of MFCs.
Recently, more emphasis has been given on resource and by-
products recovery to increase the treatment competence of BES to
match with the existing wastewater treatment processes during third
generation of BES. The by-products and resources like heavy metals,
nutrients, minerals, and industrial intermediate chemicals can be
recovered during bacteria catalyzed redox reactions. Quite large
number of research/review articles have been published to address
the different aspects of BES such as electrode materials, materials used
for components, substrates, microbes, pollutant removal, modelling
aspects, etc. to enhance the performance of BES [22]; however, few
articles (less than 1%) discussed the scope of by-products recovery
from wastewater in BES [23,24] (Fig. 2). A promising and sustainable
solution for recovery of useful chemical by-products with (or without) a
provision to generate renewable energy in the form of electricity can be
offered by BES. Dual purpose of BES i.e. energy generation and
Fig. 2. Number of publications of the different modifications in bio-electrochemical
system (Scopus data, accessed on January 15, 2017) [22].
D.A. Jadhav et al.
bioremediation makes BES more attractive to the researchers.
However, to make it more practical for real life application and positive
energy gain, the recovery of by-products from wastewater should be
focussed. Considering existing research gaps, this review emphasizes
on recovery of useful chemical by-products from wastewater, which will
be a major breakthrough in BES research to encourage its application.
This article is an effort to contribute knowledge towards production of
value-added and important chemical by-products, their mode of
synthesis and recovery while treating wastewater in BES.
The recovery of by-products during bio-electrochemical reactions
reduces additional energy requirement for individual by-product
synthesis processes. The major technological breakthrough is the
possibility to apply external voltage as the driving force in MEC during
microbial electro-catalysis to accelerate the production of high value
reduced chemicals such as methane, hydrogen gas, caustic soda or
hydrogen peroxide at the cathode, at a much lower energy cost [25–
27]. Higher market value of these reduced by-products in comparison
with the cost of applied electrical potential to produce them makes BES
technology economically more attractive. Subsequently, electricity-
driven processes have also been applied and widely explored in the
context of bioremediation and inorganic/resource recovery. Studies on
life cycle assessment (LCA) or Cradle-to-gate analysis represents that
the recovery of high value products from well-designed BES can
provide significant environmental benefits [28]. Thus, BES has poten-
tial to offer a promising solution for recovery of products, other than
bio-electricity, through different mechanisms as discussed here in
details.
2. Production and recovery of high-value end-products from
BES
2.1. Recovery of inorganic materials
2.1.1. Heavy metal recovery
Heavy metals present in industrial effluents pose a serious problem
to the environment and public health, since many of these metals are
toxic even at low concentrations. Physical, chemical, and biochemical
technologies for heavy metals removal from wastewater have been
developed, and further efforts have been made for its possible recovery.
Such treatment processes can be made cost-effective and sustainable by
facilitating metal recovery using BES. Moreover, BET has ability to
remove and recover metals even when present at very low concentra-
tion in aqueous medium, making it an economically viable option than
other alternative processes.
Direct reduction of metals having redox potential (vs. SHE) higher
than the potential of biotic anode to impose thermodynamically
favourable reaction kinetics was studied, where the electrons generated
in anode are directly consumed by abiotic metal cathode such
as Cu2+(E0ʹ=0.337 V), Fe3+(E0ʹ=0.770 V), Au3+(E0ʹ=1.001 V),
5+ 0 4+ 0 + 0ʹ
V (E ʹ=0.991 V), Cr (E ʹ=1.330 V), Ag (E =0.799 V) and
Hg2+(E0ʹ=0.911 V) without external power supply [29]. Few studies
showed recovery of metals with lower redox potential, such as
Ni2+(E0ʹ=0.250 V), Pb2+(E0ʹ=0.130 V), Cd2+(E0ʹ=0.400 V) and
Zn2+(E0ʹ=0.762 V), by using biotic anode and abiotic cathode under
the influence of external power source to force the movement of
electrons from anode to cathode side (Table 1). Higher reduction rate
of chromium and other transition metals can be achieved under the
assistance of microbial metabolism at bio-cathode with or without
poised potential [30].
A sustainable self-driven MFC-MEC based treatment has been
studied for recovering Cr4+, Cu2+ and Cd2+, when their initial feed
concentration was fixed to 5 mg/l, which showed complete recovery in
MEC with simultaneous bioelectricity generation in MFC [31]. For
heavy metals removal from fly ash leachate, Tao et al. [32] designed a
hybrid system of BES and electrolysis reactors in which Cu (II) was
recovered in the form of Cu2O during cathodic reduction (Eq. (1));
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Renewable and Sustainable Energy Reviews 76 (2017) 1022–1031
whereas, Zn and Pb were recovered during electrolysis (Eqs. (2) and
(3)) and found a respective removal of Zn, Cu and Pb as 95.4%, 98.5%
and 98.1% at 25 °C.
Cu2++2e−→Cu (E0= 0.337 V)… (1)
Zn2++2e−→Zn (E0= −0.762 V)… (2)
Pb2++2e−→Pb (E0= −0.130 V)… (3)
Moreover, the metal assimilation and dissimilation mainly depends
on interactions between microbes and metals in BES. Hence, the novel
approach of BES can provide solution for effective metal recovery
through redox reactions.
2.1.2. Iron oxide recovery
Iron oxide compounds, recovered from red-mine mud, have been
found to be an inexpensive and effective option as catalysts for fuel cell
applications [33–35]. The novel approach of MFC was used to treat
wastewater (acid mine drainage, AMD) along with simultaneous
electricity generation, using microbes as biocatalyst. A dual-chamber
MEC was developed to concurrently produce H2 and recover heavy
metals like Cu2+, Ni2+, and Fe2+from AMD with single and mixed metal
present in the solution [34].
Cheng et al. [36] developed a chemical fuel cell for treatment of
AMD containing Fe2+ ions in the anodic chamber, and demonstrated
considerable power generation of 290 mW/m2 (7.2 W/m3) under a
thermodynamically favourable condition along with successful metal
recovery (Fe2+ to Fe3+) (Eq. (4)). During oxidation in fuel cell, ferrous
iron present in AMD was completely removed to insoluble ferric iron,
forming a precipitate at the bottom of the anodic chamber as well as on
surface of the anode. Around 99% iron removal with Coulombic
efficiency of 19% at pH of 7.9 during treatment of AMD in cathodic
chamber of MFC has also been obtained by Lefebvre et al. [37].
Fe2++3H2O=Fe(OH)3↓+3 H++e– (Ecell0=0.28 V;
ΔG°= − 27.15 kJ/mol)… (4)
2.1.3. Elemental selenium recovery
Selenium is a mineral found in soil, water and some foods. MFC can
convert significantly high concentration of dissolved selenium in
selenate (Se (VI), SeO42−) and selenite (Se (IV), SeO32−) form, present
in wastewater streams of glass manufacturing and electronic industrial
effluents, to its elemental form Se(0) [38,39]. Microbial reduction of
soluble selenium oxy-anions into insoluble elemental selenium is a key
process exploited in the biological treatment of wastewater contami-
nated with selenium. Lee et al. [40] reported that facultative anaerobic
Shewanella sp., well known for their capability to generate electricity in
MFCs, were able to utilize selenite as the sole electron acceptor during
their respiration under anaerobic conditions. This theory resulted in
reduction of selenite from wastewater and deposition of bright red
nano-sized spherical particles of elemental Se (Eq. (5)) over the anode
as well as the water facing side of the cathode in an air-cathode MFC,
demonstrating around 99% of selenite reduction [36].
Se4+ (aq.) + 4e− → Se0 (ECell
0
=0.41V)… (5)
2.1.4. Uranium recovery
The study was conducted by Gregory and Lovely [41] with imposed
potential of −500 mV (vs. Ag/AgCl) to graphite cathode, where they
were able to recover 87% uranium from uranium−contaminated
subsurface sediments in biotic cathodic chamber. The pure culture of
Geobacter sulfurreducens recovered uranium by reducing soluble
U(VI) oxidation state to the relatively insoluble U(IV), with organic
compounds serving as the electron donor during bioremediation of
contaminated soil and groundwater collected from uranium ore
D.A. Jadhav et al. Renewable and Sustainable Energy Reviews 76 (2017) 1022–1031

Table 1
Review on metal recovery from wastewater using BES.

Metal Concentration (mg/l) Removal (%) Power density Remarks References

Cr 204 99.5 1.6 W/m2 Real electroplating *WW treatment [105]

V 250–1000 26.1 0.97 W/m2 Pollutant removal [106]
Au3+ 200 – – Electro-deposition [107]
Ag 50–200 99.91 4.25 W/m2 *WW with Ag ions [108]
Cu 1000 97.8 0.536 W/m3 CuSO4 catholyte [109]
Se 200 98 12.8 mW/m2 Constructed Wetland MFC [110]
Cd 200 mM 90 3.6 W/m2 Single chamber membrane−less MFC [111]
Zn 400 mM 97
Fe 500 99 8.6 W/m3 Dual chamber MFC [37]
Hg 25–100 90–99.3 0.433 W/m3 HgCl2 [112]
Ni 50–1000 99 – Abiotic cathode with external voltage [113]
Pb 400 47.5 – External voltage [114]

*WW=wastewater.

processing facility. Bioremediation of uranium has also been suggested
by converting toxic soluble U(VI) to insoluble U(IV), which was
precipitated as UO2onto the surface of cathode during electrochemical
reduction (U6+/U4+: ECathode=−0.042 V) [42]. Thus, BES can also be
utilized as a bioremediation system for soluble radioactive material
recovery from contaminated water.
2.2. Nutrients recovery
Nutrient removal from wastewater has become a key challenge for
many of the treatment processes. The nutrient removal and recovery
from urine and swine wastewater can be carried out by adopting
biological approaches in BES [5,43–46]. Urine can be considered as an
ideal fuel (source of C, P, N, and K) for electricity production in MFC.
The potential energy and ammonia recovery from urine using a BES
was explored by Kutke et al. [47] and Ieroupolos et al. [48]. Ammonia
recovery in MFC was done by treating urine in the anodic chamber and
migration of ammonium ions by diffusion towards cathodic chamber
was followed by subsequent absorption [47]. Higher current density of
3.6 A/m2 and significantly improved recovery of NH4+ ions by 61% in
MFC was reported in a microbial electrochemical cell under electricity-
driven migration [49].
Swine wastewater is rich in phosphate and thus, its treatment is a
crucial issue. Struvite (NH4MgPO4·6H2O) precipitation on the cathode
surface and phosphate recovery up to 27% with phosphate removal
efficiency of 70 – 82% was reported in BES [50,51]. Recovery of
orthophosphate (600 mg/l) as fertilizer from digested sewage sludge
was carried out along with generation of bio-electricity in MFC by the
metabolic activity of Escherichia coli [52]. Hence, application of BES
for ammonium and phosphate recovery with simultaneous energy
production from urine and swine wastewater is possible.
A novel approach for treating high strength sulphate wastewater by
bio-electrochemical processes has been reported by Blázquez et al.
[53]; where, the enrichment of bio-cathode with autotrophic sulphate
reducing bacteria (SRB) and sulphide oxidizing bacteria (SOB) leads to
recovery of elemental sulphur during the bacterial metabolic process.
By utilizing in-situ generated H2 as electron donor, the reduction of
sulphate by SRB was observed in the cathodic chamber producing H2S
[54], achieving sulphate reduction rate of 388 mg. S−SO42−/(l. day).
Also, water was dissociated in anodic chamber to produce oxygen,
which travelled to cathodic chamber through anion exchange mem-
brane and provide aid to SOB for catalysing the H2S oxidation to
produce elemental sulphur which gets deposited on the cathode
surface.
2.3. Production of algal biomass
Algal biomass generated during photosynthetic activities of algae
can be used as a direct source of organic matter for electricity
generation in MFC and production of bio-fuels [5,55].
Photoautotrophic microorganisms tend to produce organic compounds
by using CO2 as a carbon source during carbon capture and storage
process in microbial solar cell. Furthermore, the photosynthesis
process could be encouraged in the cathodic chamber to supply oxygen
for cathodic reduction and production of algal biomass as a by-product.
The recovered algal biomass can effectively serve as a substrate in
photo-bio-electrochemical cells, after different pre-treatments with
heat, microwave, ultrasonic waves, acidic and alkaline chemicals, and
even with the residue separated after extraction of algal oil [56].
Possibility of algal biomass recovery was previously reported by using
microbial carbon capture cells, where sequestration of carbon dioxide
can be achieved by sparging the produced anodic CO2 gas into
catholyte, containing Chlorella vulgaris algae, forming a bio-cathode
[57,60]. Furthermore, algal biomass of marine algae Chaetoceros sp.
has the potential to inhibit the growth of methanogens present in the
mixed inoculum and also it can be utilized as a substrate for anodic
oxidation in MFC [58].
3. Recovery of intermittent bio-chemical compounds from
BES
3.1. Industrial chemicals/gases
Principally, MFC operation is targeted to harvest maximum energy
in the form of electricity; however, the major fraction of energy is lost
because of generation of methane and hydrogen gas. Performance of
microbial bio-cathode was evaluated for the recovery of methane by
reduction of carbon dioxide in cathodic chamber of MEC, using a pure
culture of Methanobacterium palustre. It demonstrated higher rate of
methane generation up to 0.055 mol/(gVSS. day) and electron capture
efficiency (over 80%) by hydrogenophilic methanogenic culture.
Methane was produced via both abiotically produced hydrogen gas
(i.e. hydrogenophilic methanogenesis) by direct extracellular electron
transfer and also during biological fermentation of organic matter [59].
The major incidences of methane production in MECs have been
reported using hydrogen gas produced during the process by hydro-
genotrophic methanogenesis. The CO2 generated during acetoclastic
methanogenesis is used by hydrogenotrophic methanogens to produce
methane (CH4) gas. The gases like H2, CO2, CO were recovered from
wastewater using combination of MFC-MEC system and can be utilized
further for industrial applications [60,61].
An emerging BET for cost effective production of hydrogen
peroxide (H2O2), an important industrial chemical, and simultaneous
co-products generation valorised the grey water and black water
treatment [29,62,63]. Production of H2O2 along with electricity in
MFC is a theoretically feasible process over a cell voltage of 0.58 V;
however, the production rate is significantly lower. Moreover, when a
voltage of 0.5 V (vs. SHE) was imposed, H2O2 was shown to be

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D.A. Jadhav et al.
Fig. 3. Electro-catalytic reduction reactions for bio-fuel conversion in BES.
recovered at the rate of 1.9 ± 0.2 kg H2O2/m3 day from acetate with
83.1 ± 4.8% of cathodic reduction efficiency of oxygen in MEC [64]. The
reduction reaction was facilitated by providing thermodynamically
favourable conditions to support the redox potential for overall
reaction.
Lower cathodic overpotential and higher cathodic recovery for bio-
catalytic reduction of CO2 to fuel gas CH4 can be facilitated either by
direct or indirect extracellular electron transfer (EET), as discussed by
Eerten-Jansen et al. [65]. The direct pathway of EET (ECat=−0.24 V vs.
SHE) was found to be more energy-efficient process in MEC than MFC.
At a cathode potential of −0.55 V vs. SHE, Cheng et al. [66] found the
rate of methane recovery as 0.006 m3/(m3 day) in a methane producing
MEC using acetate based synthetic wastewater (COD of 1 kg/m3) as an
electron donor in anodic chamber. A similar study of bio-catalyzed
electrolysis as a novel biological H2 production process demonstrated
an approximate hydrogen generation of 0.02 m3/(m3 day) in cathodic
chamber (Fig. 3) at an applied voltage of 0.5 V, when acetate was fed in
the anodic chamber [67,68].
The urea bioreactor electrochemical system in combination with a
forward osmosis subsystem removed more than 80% of organic
carbons and recovered approximately 86% of the urea to ammonia
(Eq. (7)) [69]. A granulated activated carbon (GAC) urease bioreactor
was used to recover urea from human urine and to convert it to
ammonia. In the bioreactor, the urea reacts with immobilized urease to
form ammonia and carbolic acid (Eqs. (6) and (7)). The produced
ammonia was injected to an electrochemical cell to generate direct
electrical energy. Electrochemical cell was capable to oxidize ammonia
molecules to produce molecular nitrogen and water (Eq. (7)), along
with generation of six electrons during conversion of every two
ammonia molecules.
Enzymatic hydrolysis (with urease) of recovered urea:
CO(NH2)2 +2 H2O − − − → 2NH3 + H2CO3…
Oxidation of ammonia:
2N H3+6OH−− − − →N2+6 H2O + 6 e−…
3.2. Ethanol recovery
Beyond the general lignocellulose-to-ethanol pathway, a novel
method of bio-electrochemical conversion of waste biomass to liquid
ethanol fuel by biological acetate reduction with hydrogen and bio-
Renewable and Sustainable Energy Reviews 76 (2017) 1022–1031
Fig. 4. Bio-electrochemical conversion of acetate to ethanol in MEC.
cathode as an electron donor has been previously investigated by
researchers [70–72]. A recent study with dual chambered MEC,
equipped with three electrode system, a working electrode (WE –
cathode), a reference electrode (RE) and a counter electrode (CE –
anode), was configured and operated at constant cathode potential of –
0.55 V vs. SHE (Fig. 4); whereas, the anodic reactions prevailed with
the oxidation potentials of ferro-ferricyanide redox couple (Eqs. (8)–
(10)). In the presence of mixed consortia, specific electron mediators
like methyl viologen and imposed potential (–0.55 V vs. SHE) in
cathodic chamber of MEC, the study successfully recovered 83 mg/l
of ethanol [73,75] from 50 mM acetic acid. Similarly, Steinbusch et al.
[75] reported the recovery of carbon rich compounds like ethanol and
butanol in the cathodic chamber. Also, the novel use of mediators to
accelerate electron transport from cathode to bacteria, to influence
their metabolism and hinder the parasitic reactions like methanogen-
esis, which can increase the undesirable butyrate concentration (Eq.
(11)), were also discussed in the same study. The details of the half-cell
reactions are summarized below:
Anodic reactions [77]:
Fe(CN )64− → Fe(CN )3− − 0
6 + e (EA = –0.360 V )… (8)
Cathodic reactions:
Desirable reactions –
CH3COO−+ 5H++4e−→CH3CH2OH + H2O (EC0= – 0.408 V [73]) …(9)
2 H++2e−→H2… (10)
Undesirable reaction –
2CH3COO−+5H++4e−→CH3(CH2)2COO−+2H2O … (11)
(6) 3.3. Medium chain triglycerides − the biological precursors of
renewable fuels
(7) Medium chain fatty acids which are naturally present in food, used
in medicine and food products, can be recovered in BES to impart
greater benefits [78]. Recently, researchers investigated the mechanism
of producing medium chain fatty acids with a higher length than
butyrate from acetate in BES with (or without) using external electron
mediators and cathodic electron donors [74,79]. An in-situ supply of
electrons was mediated by the cathodic microorganisms that produced
ethanol by utilizing hydrogen (H2 production pathway) or directly by
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D.A. Jadhav et al.
cathode through bio-electrochemical hydrogen production.
A novel pathway of reduction of acetate by using H2 as an electron
donor to produce medium chain fatty acids, caproate (C−6) and
caprylate (C−8), having a superior physical properties as a precursor
to fuels and chemicals compared to ethanol and VFA, was discovered
(Eqs. (12)–(15)). Few past studies exhibited the production of C2–C8
fatty acids and ethanol in MEC operated at an applied cathode
potential of –0.9 V vs. SHE [74–77]. Configuration of MEC used was
similar as depicted in Fig. 4 and 100 mM acetic acid was used as
catholyte for production of medium chain fatty acids caproate and
caprylate from acetate. Bio-electrochemical production of caproate
(739 mg/L), caprylate (36 mg/L), butyrate (263 mg/L) and ethanol
(27 mg/L), respectively, was reported by Eerten-Jansen et al. [74]
during intermediate reduction of organics. Ethanol was produced by
mixed culture of anaerobic bacterium, predominantly obtained as
Clostridium kluyveri, Eubacterium pyruvativorans, Clostridium tyr-
obutyricum etc., in the cathodic chamber, thus avoiding its external
addition in this study. The thermodynamic feasibility of step-wise
reaction mechanisms are discussed below.
Ethanol production via H2 pathway:
CH3COO−+5 H++4 e−− − − →CH3CH2OH+H2O(E0 = – 0. 408
V vs. SHE) … (12)
Reduction of acetate to butyrate−intermediate and conversion to
caproate and caprylate:
2 CH3COO−+ 6 H ++4 e−− − →CH3(CH2 )2 COO− + H ++2 H2O… (13)
Caproate production:
CH3CH2OH + CH3(CH2 )2 COO−− − − → CH3(CH2 )4 COO− + H2O…
(14)
Caprylate production:
2CH3CH2OH + CH3(CH2 )2 COO−− − − → CH3(CH2 )6 COO− + 2H2O…
(15)
3.4. Biopolymer synthesis
Polyhydroxyalkanoates (PHAs) having rheological properties simi-
lar to polypropylene, are a naturally degradable bio-plastics extracted
from bacterial cells. However, high production cost of PHAs over the
low cost petro-chemically derived plastics led to less importance in its
production and research [80–82]. Recent researches on bio-electro-
synthesis of PHAs have created a renewed interest, demonstrating its
production in cathodic chamber under ample availability of carbon and
nutrient sources [25,83]. Also, PHA synthesis pathway by cathodic
micro-aerophilic biofilm, utilizing CO2 as the carbon source in BES,
evidenced the yield of alcohols, carboxylic acids, diols and biopolymers
such as poly−β−hydroxybutyrate, when an enforced cathodic reduction
potential was implied by external power supply [84]. This concept was
further developed by Srikanth et al. [85], demonstrating enhanced
electrogenesis and accumulation of synthesized PHA in the cathodic
chamber of MFC using aerobic consortia as biocatalyst.
3.5. Biorefinery intermediates
Hydrolysates produced by hydrothermal treatment of lignocellulosic
feed-stocks, originating from agricultural and bio-refinery facilities, can
be considered as a potential source of substrate in BES. It results in
formation of high value reaction intermediates of poly-phenolic lignin,
cellulose and hemicellulose residues upon further treatment [86–88].
Reduction of such reaction intermediates can be facilitated by hydrogen
produced in cathodic chamber of MEC, finally yielding the poly-phenolic
group of metabolites (equol and resveratrol), which is widely used as a
natural antioxidant and composite material for bio-plastics [72,89–91].
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Renewable and Sustainable Energy Reviews 76 (2017) 1022–1031
4. Hybrid approach of wastewater treatment for efficient co-
product recovery
With development in BES research, several studies came with an
integration of one or more wastewater treatment processes with BES to
increase the effluent quality and recover maximum available energy
present in the wastewater. The products such as bio-hydrogen, bio-
methane, electricity, bio-fertilizer, caustic soda, hydrogen peroxide, etc.
were formed during the integrated operation of hybrid BES. Hydrogen
and methane production during such combined operation makes the
hybrid system more attractive and efficient [92]. A methane producing
MEC in combination with anaerobic digestion has been proposed as a
polishing post-treatment for effluent received from anaerobic digesters
[93]. The hybrid approach of MFC with anaerobic membrane bior-
eactor [94], integrated photo-bioreactor fuel cell [95], anaerobic
digester (AD) [96], up-flow anaerobic sludge blanket reactor (UASB),
MEC, rotating biological contactor [97], desalination cell [98], etc. were
investigated to produce higher quality treated effluent and recover
valuable by-products [9] (Fig. 5). With respect to energy production,
assuming that the of energy recovery from the AD, MFC and algae
treatment steps are 28%, 10% and 3%, respectively, in making total
41% of the chemical energy that can be recovered, which theoretically
would turn the treatment process into a net energy producer by when
the energy consumption of wastewater treatment was less than 10% of
the energy content [99].
The hybrid system is capable to achieve higher levels of wastewater
treatment and it can provide polishing treatment as well for removal of
specific pollutants. The BES-centred hybrid treatment system is
proposed as an example of integrating bio-electrochemical technology
with relevant technologies for improving treatment sustainability.
However, it demands high energy input and additional components
to attach, which consequently increase the cost of fabrication. Also,
difficulty with reactor scaling-up and primary barrier for hybrid
systems (including MFC) due to the complexity of the combined
treatment processes, strive its practical implementation. Therefore, a
balanced evaluation and suitable modifications of all unfavourable
factors are required to be duly addressed to guide the process design
and operation of such hybrid processes.
5. Other chemical recovery options
Realizing the full poly-generation potentials, i.e. recovery of metals,
production of bio-fuels and chemicals from reuse of CO2 and clean
water from waste streams can attain an economic and environmental
upside of novel electrochemical synthesis processes. The wastewater
Fig. 5. Application layout of BES in a hybrid system.
D.A. Jadhav et al. Renewable and Sustainable Energy Reviews 76 (2017) 1022–1031

Table 2
Comparative yield and energy efficiency of biochemical compounds.

Elements Reactor/method used Removal efficiency Energy/current capture efficiency References

Organic carbon ASBR (Anaerobic sequencing batch reactor) 58% 17.7 ± 10.1% [104]
UASB (Upflow anaerobic sludge blanket) 69% 12.2 kJ/g COD
[24.0 ± 11.4%]
ABR (Anaerobic baffled reactor) 90.3% 7.3 kJ/g COD
[47.5 ± 4.5%]
AFB (Anaerobic fluidized bed) 82% 33.8 ± 12.9%
AnMBR (Anaerobic membrane bioreactor) 86.7% 9.7 kJ/g COD
[35.4 ± 26.8%]
MEC 78% 14.3 ± 14.4%
MFC 83% 0.48 kJ/g COD
[1.6 ± 1.4%]
Nitrogen HRAP (High rate algal pond) 67.1%
PBR (Photobioreactor) 78.5%
Stirred tank 62.3%
ATS (Algal turf scrubber) 70.5%
MFC 47–83% [55,115,117]
Integrated photo−bio-electrochemical (IPB) system 63% [116]
Phosphorus HRAP 52.1% [104]
MFC 27. 82% [50,55]
PBR 93.2% [104]
Stirred tank 78.2%
ATS 78.6%
MEC 20–40% [117]
CH4 CO2 to CH4 in BES (at −0.65 V EC vs. SHE) 0.055 ± 0.002 m mol/(day. mg VSS) [59]
MEC by electromethanogenesis (at < −0.7 V EC vs. Ag/ 80% 90% [33]
AgCl)
MEC (at –0.55 V EC vs. SHE) 3 3
0.006 m /(m day) 51.3% [65]
H2 Bio-catalyzed electrolysis (applied voltage: 0.5 V) 0.02 m3/(m3 day) 53 ± 3.5% [67]
Biocatalyzed electrolysis (at −0.7 V EC vs. SHE) 0.63 m3/(m3 day) 49% [68]
H2O2 BES (applied voltage: 0.5 V) 1.9 ± 0.2 kg/(m3day) 83.1 ± 4.8% [64]
Ethanol BES (at −0.7 V EC vs. SHE) 13.5 ± 0.7 mM 74.6 ± 6% [72]
Triglycerides Flat plate electrochemical cell (at −0.9 V EC vs. SHE) Caproate: 739 mg/L 26% [74]
Caprylate: 36 mg/L

treatment producing reusable quality water and carbon capture along
with recovery of sodium salt at cathode was achieved by employing the
MFC technology [96]. About 9% (w/v) sodium salt was recovered in the
form of sodium carbonate and sodium bicarbonate with use of Pt−free
cathode in MFC, which might be attributed to the oxygen reduction
reactions, water diffusion and electro-osmotic drag [100].
Recently developed technique of microbial desalination cell (MDC) has
been implemented to recover chemicals like HCl and NaOH, when a bipolar
membrane (BPM) is placed next to the anodic chamber into the MDC,
combining to form a microbial electrolysis desalination and chemical-
production cell. With application of electric field in MDC, the water
dissociation reaction resulted into generation of protons and OH− ions.
Furthermore, the H+ ions migrated into the acid production chamber
through cation exchange membrane (CEM), resulting in generation of HCl
(2.1 mM). Similarly, the generated OH− ions migrated to the anodic
chamber via anion exchange membrane (AEM) to produce NaOH
(2.6 mM), along with removal of NaCl and bio−electricity generation
[46,98,101]. In microbial electro-synthesis system (MES), the stillage
streams from bio-refineries can be effectively used as a substrate to recover
value added products; hence, coupling of MES with waste refineries can be
useful to increase the efficiency of recovery of resources [102]. In BES, the
mixed microbial community growing on the cathode can convert glycerol
reductively to 1,3−propanediol [103]. They presented a combined approach
for 1,3−propanediol production and propionate extraction in three cham-
ber reactor system, which leads to recovery of additional 3−carbon
compounds in BES.
6. Perspectives
In about one decade of research and development in the field of
environmental electrochemistry, the functionality of microbial electro-
chemical technologies has expanded dramatically with modified and
improved performance. Along with the main products (hydrogen,
electricity, etc.), BES shows capability of recovering other valuable
products such as heavy metals, nutrients, industrial chemicals and
gaseous fuels. As discussed in this review article, BES carries great
prospects for resource recovery; however, some biotechnological
barriers and economic challenges are yet to be solved before it can be
implemented at large scale and to be considered as an attractive
alternative to the existing wastewater treatment methods.
The negative energy balance of present wastewater treatment
systems can be reversed if BES technology is utilized to recover the
energy from organic carbon and phototrophic technologies are im-
plemented for nutrients and other by-products recovery [104]. Based
on the life cycle assessment (LCA) studied by Foley et al. [28],
performance of MFC needs to be improved to produce more power,
so as to establish it as a commercially viable and competitive solution
comparable with existing anaerobic treatment technologies. This
particularly demands attention in developing the low cost catalysts
and efficient electrode materials to accelerate the oxygen reduction
reaction on cathode for reducing the cathodic overpotential and to
support higher current densities.
The production efficiency (or yield efficiency) of inorganic nutrients,
heavy metals and organic chemicals by the aforementioned mechan-
isms in BES are listed in Table 2. Major BES studies have been
conducted in laboratory scale and the technology is still having
profound limitations for real world applications for wastewater recla-
mation and recovery of resources. However, further research efforts are
required to upgrade the performance of BES by modifying the
electrodes and separator assembly with low-cost, fouling resistant,
conductive and bio-compatible materials to reduce the kinetic losses
and develop a deeper understanding of bio- electrochemical processes
to enable process optimization. Detailed economic and possible life
cycle analyses are essential to understand the costs and benefits of
specific resource recovery processes by BES, before scaling up for real-
world applications. Future studies should emphasize more on resource

1028
D.A. Jadhav et al.
recovery to make the energy balance positive and develop better
understanding of related mechanisms.
7. Conclusion
Bio-electrochemical system (BES) has been widely investigated for
electrical energy recovery, bioremediation, intermediate chemical
production and recently, for useful resource recovery. This review
mainly emphasized on third generation of BES research for its
potential to recover the other by-products i.e., heavy metals, nutrients,
industrial chemicals, etc. from the wastewater. The recent development
of bio-electrochemical technology offers a flexible platform for both
oxidation and reduction oriented reactions leading to recovery of value
added products while treating wastewaters. Further efforts are neces-
sary to develop better understanding of the different mechanisms of
resources recovery and the economic feasibility of engineering applica-
tions of field-scale BES technology.
Acknowledgements
The research is supported by the Grant received from Department
of Science and Technology, Government of India (File no. DST/TSG/
NTS/2010/61). Also, the fellowship received to S. Ghosh Ray from
Ministry of New and Renewable Energy, Government of India (Ref. no.
10/14/2010-P & C) is duly acknowledged.
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