Journal of Environmental Chemical Engineering 11 (2023) 110021

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Journal of Environmental Chemical Engineering

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A review on bioelectrochemical systems for emerging pollutants

remediation: A computational approaches
Shabnam Ahmadi a, Abbas Rezae a, *, Soumya Ghosh b, Alhadji Malloum c, d, Artur Banach e
a
Department of Environmental Health Engineering, Faculty of Medical Sciences, Tarbiat Modares University, Tehran, Islamic Republic of Iran
b
Department of Genetics, Faculty of Natural and Agricultural Sciences, University of the Free State, Bloemfontein 9301, South Africa
c
Department of Chemistry, University of the Free State, PO BOX 339, Bloemfontein 9300, South Africa
d
Department of Physics, Faculty of Science, University of Maroua, PO BOX 46, Maroua, Cameroon
e
Department of Biology and Microbiology of Microorganisms, Institute of Biological Sciences, The John Paul II Catholic University of Lublin, Konstantynόw 1I Str, 20-
708 Lublin, Poland

A R T I C L E I N F O A B S T R A C T

Editor: Dr. Y. Liu A wide range of pollutant compounds are discharged into the environment that they need suitable remediations.
For solving the problem, the bioelectrochemical systems (BESs) are green technology suitable for the pollutant
Keywords: treatments. The induced electric current in BESs can stimulate microbes metabolism and increasing electron
Bioelectrochemical systems transfer. It has been reported that the performance of BESs in reducing wastewater emerging pollutants (EPs)
Emerging pollutants
reaches more than 90 %. In the BESs, the emerging pollutants as carbon sources plays a significant role between
Computational approaches
competition and bacterial community and their metabolism. Although some BESs have been presented for the
Bio-Kinetics
Microbial metabolism treatment systems, little attention has been paid to the computational approaches and kinetics studies of EPs
remediation. Therefore, the current review summarizes the application of BESs for emerging pollutants removal.
Moreover, we have provided the predominant microorganisms as well as the microbial metabolism and
computational approaches in the biodegradation of EPs. In this review, density functional theory (DFT), mo­
lecular dynamics (MD) simulations, computational fluid dynamics (CFD), artificial intelligence or artificial
neural networks (ANNs), and quantum mechanics/molecular mechanics (QM/MM) simulations have presented
for the BESs. For interpretation of the BESs Michaelis-Menten, First-order kinetic and second order models are
suitable kinetic models.

energy sources for energy production. These green methods include

bioelectrochemical systems (BESs) being preferred to other traditional
1. Introduction methods because they have been proven to be efficient in both the
treatment of pollutants and generating electricity [2]. The bio­
Water shortages and their low quality may be compensated by electrochemical processes use active microorganisms to catalyze elec­
effective wastewater treatment to reuse water. The conventional trochemical reactions, thus BESs are recognized for wastewater
methods have some disadvatages such as low efficiency for the recalci­ treatment [5]. The BESs have some advantage and disadvatages. Low
trant compounds and high electrical energy counsumption. For example, start-up time, low energy consumption and high efficiency in removing
the application of aerobic activated sludge for treating 1 m3 of waste­ EPs are among the advantages of these systems. The need for advanced
water consumes 0.6 kWh of energy [1]. Therefore, green and environ­ equipment and expert operators for management are the major prob­
mentally friendly technologies for wastewater treatment is one of the lems of the BESs.There are following BESs systems: Microbial Fuel Cells
important challenges today. Moreover, current energy demand for (MFCs), Microbial Solar Cells (MSCs), Microbial Electrolysis Cells
humans’ needs is mainly met by the combustion of fossil fuels which (MECs), Enzymatic Biofuel Cells (EBCs), Microbial Reverse Electrodial­
causes the release of many air pollutants, especially carbon dioxide, into ysis Cells (MRCs), Microbial Electrosynthesis Cells (MDC),and Microbial
the environment [2]. Concerns about the increasing emission of pol­ Desalination Cells (MDC) combining microbial metabolism with redox
lutants, global climate change and energy shortages have led to the reactions [6]. Fig. 1 shows the steady and rapid annual increase the
expansion of studies on the use of green chemistry and new renewable

* Corresponding author.
E-mail address: [email protected] (A. Rezae).

https://doi.org/10.1016/j.jece.2023.110021
Received 21 December 2022; Received in revised form 4 April 2023; Accepted 27 April 2023
Available online 27 April 2023
2213-3437/© 2023 Elsevier Ltd. All rights reserved.
S. Ahmadi et al. Journal of Environmental Chemical Engineering 11 (2023) 110021

Nomenclature MECs Microbial Electrolysis Cells

MD Molecular Dynamics
ABQ Arylamine-1,4-Benzoquinone MDC Microbial Desalination Cells
AC Alternating Current MEC Microbial Electrosynthesis Cells
ANNs Artificial Neural Networks MFCs Microbial Fuel Cells
BESs Bioelectrochemical Systems MRCs Microbial Reverse Electrodialysis Cells
CPCM Conductor-Like Polarizable Continuum Model MSCs Microbial Solar Cells
CFD Computational Fluid Dynamics OM Organic Matter
DC Direct Current PEM Proton Exchange Membrane
DFT Density Functional Theory QM/MM Quantum Mechanics/Molecular Mechanics
EABs Electrochemically Active Bacteria SEM Scanning Electron Microscopy
EBCs Enzymatic Biofuel Cells SWCNTs Single Wall Carbon Nanotubes
Eps Emerging pollutants XPS X-ray Photoelectron Spectroscopy
FTIR Fourier Transform Infrared Spectrometry XRD X-ray Diffraction
LDA Local Density Approximation

[8]. Studies have shown that BESs can remove environmental pollutants
such as antibiotics, dyes, estrogens, organic chlorine, malic acid, phe­
nols, surfactants, acetate, cellulose, heavy metals, sulfate, sulfide, and
radio nuclides such as uranium [8–11] as well as for recycling nutrients
and micro pollutants from wastewater [3,4,8]. The principle of oper­
ating all BESs is the electrochemical activity of microorganisms and use
of OM as electron donor for energy production and recycles pollutants
[12]. The results of studies showed 98 % efficiency for ammonium
removal and 81 % for COD removal in the treatment of a nitrogen-rich
wastewater under optimal conditions using single-chamber MFCs in
bio-anode structures for electron transfer to electrodes of active bacteria
[3,13]. Other studies have shown that BESs have advantages such as
cost-effective performance in high antibiotic removal, and that this
process is environmentally friendly because pollutants are mostly
degraded in MFCs and also do not produce highly toxic by-products
[14]. One method of biodegradation of environmental pollutants is to
increase microbial metabolism using bio-stimulation. One way of mi­
crobial stimulation is to use electrical stimulation to enhance metabolic
pathways [15]. Research has been performed to directly and indirectly
Fig. 1. The articles on the BESs (Web of Science database).
stimulate microbial metabolism by electric current [16]. Induced elec­
tric current produces energy for microbial respiratory processes and
articles published on the MFCs and MECs showing the highest peak from
stimulates the biodegradation of pollutants [17]. Therefore, the current
2010 to 2019 (Fig. 1) [7]. Microorganisms operating in BESs decompose
review summarizes the application of BESs for pollutants removal,
organic compounds using them as electron donors in the anode chamber
including several emerging pollutants (EPs). Notably, both water and
due to their electrochemical activity followed by the produced electrons
wastewater are also being identified with the challenges and perspec­
transfer to the cathode chamber [8,9]. Generally, cationic membrane
tives that contribute to achieve this goal. The density functional theory
separates anodic and cathodic chambers. This membrane has selective
(DFT), molecular dynamics (MD) simulations, computational fluid dy­
permeability to protons (H+) and is impermeable to anions, electrons,
namics (CFD), artificial intelligence or artificial neural networks
and oxygen [10,11]. If the anodic reaction is catalyzed by microbes as it
(ANNs), and quantum mechanics/molecular mechanics (QM/MM)
is called as bioanode, while the cathodic reactions catalyzed by microbes
simulations were studied too. we examine the predominant microor­
it is known as biocathode [12,13]. In BESs chemical energy is directly
ganisms as well as the microbial metabolism in degradation of emerging
converted into valuable resources through microbial catalysis, such as
pollutants (EPs). This review will help researchers to identify strengths
production of hydrogen in the MECs and electricity in the MFCs. MDC
and weaknesses and help to shape future research on this aspect.
can be used simultaneously to remove salts, generate electricity and
remove contaminants [5]. However, MFCs and MESs are the most
2. Emerging pollutants (EPs)
advanced and widespread BESs. Although there is no rationale to use
MFCs for electricity generation in wastewater treatment, it is more
Extensive discharge of chemical compounds into water and soils
attractive to remove organic waste with this more sustainable technol­
started the discussion on their impact on environment quality and
ogy [3,4]. In this regard, the exploitation of wastewater as energy source
human health as even present in such low concentrations as ng L− 1 to mg
and substrates for production of valuable chemicals on site is more
L− 1 may significantly contribute to the pollution. These chemicals of an
realistic in MEC/MESs [5]. In MFCs, when electrons reach the cathode
emerging concern and often anthropogenic origin are termed as
under aerobic conditions they combine with protons and oxygen even­
Emerging Pollutants (EPs) or pollutants of emerging concern (PEC)
tually forming water molecule [6]. In the absence of oxygen the elec­
[18–20]. This group of hazardous compounds consists of both organic
trons combine with the protons to break down the organic matter (OM)
and inorganic substances being both natural and/or synthetic in origin
in the anode chamber leading to hydrogen production when reaching
(industry, agriculture, domestic). The examples of EPs are: pharma­
the cathode [7]. Due to the fact that microorganisms degrade the sub­
ceuticals, hormones, personal care compounds, pesticides, surfactants,
strate, BESs may be used for the removal and recycling of contaminants
flame retardants, micro plastics, other products of chemical industry,

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S. Ahmadi et al. Journal of Environmental Chemical Engineering 11 (2023) 110021

heavy metals and nano-compounds [18–21]. What’s more, there are also 4-benzenediamine and 1,4-benzenedithiol combined with short gold
EPs of biological origin including pathogenic bacteria, viruses and electrode. The authors have used three layers of gold and applied 10 mV
protozoa [21]. Pharmaceuticals besides treating diseases/illnesses can to the electrodes showing the effects of the conformational change and
have side-effects on non-target species when discharged into environ­ bonding states on the local transmission pathways [25]. To develop
ment, in addition a lot of waste materials are released during their efficient D-fructose biosensor, Voitechovič et al. [26] have investigated
production (e.g. solvents, oxidizers, reactants, catalysts) forming a seven derivatives of 2-arylamine-1,4-benzoquinone (ABQ), both exper­
serious source of pollution. Agrochemicals (pesticides, hormones) may imentally and theoretically. ABQ derivatives are used to develop bio­
leach to surface- and groundwater entering food chain what may have electrochemical systems. The theoretical investigations have been
negative effects for living organisms [21]. Heavy metals, including lead, performed using DFT. Optimization of the structures has been carried
cadmium, mercury, arsenic, zinc, copper and nickel as well as out using the B3LYP DFT functional associated with the 6–311 +g(d,p)
nano-materials can have cancerogenic action for living organisms [18]. basis set. The solvent phase has been modelled using the conductor-like
The concerns about EPs result from their properties, most of them is polarizable continuum model (CPCM) [26]. For accurate free energy
polar, what makes them dissolve in water. In that way they can be calculation, the frequencies have been scaled with a scale factor of
transported between various environmental compartments. In addition, 0.9877. The calculated properties of the derivatives show that the
EPs may be easily accumulated in biomass (biomagnification), enter electron transfer between the ABQ derivatives and the electrode is
food chains, what together with their resistance to biodegradation evaluated to be around 100 mV [26]. Furthermore, other authors have
makes them recalcitrant substances forming severe health and envi­ also applied DFT to study the conformational change of bio­
ronmental risks [18,19]. The examples of health issues caused by such electrochemical molecules interacting with the surfaces of electrodes
substances are cancers, DNA mutations, hormonal system dysfunction, [27,28].
gastrointestinal toxicity, infertility and other [22]. Another problem
with EPs is not clear legislation about reduction their levels in water. 3.2. Molecular dynamics (MD) simulations
Some on them are included on the lists of priority of European Union
(EU 2013/11/EU) or WHO(2017) [23] but not always properly moni­ Molecular dynamics (MD) is another computation approach based on
tored or regulated[24] resulting in very broad distribution of these molecular simulations that has been used to study bioelectrochemical
compounds in many environmental compartments which need to be systems. It is worth noting that only a few studies have been reported
treated [20]. using MD simulations. Liu and co-workers reported molecular dynamics
simulations to simulate the conformational mobility mechanism of the
3. Computational studies on bioelectrochemical systems (BESs) coenzyme of glucose oxidase. The simulations have been performed
using the CHARMM27 force fields. Both NAMD and GROMACS pro­
Simulation of bioelectrochemical systems is a complex task requiring grams have been used for the simulations [29]. The authors have studied
combination of several computational steps for their simplest process. four positions of glucose oxidase as adsorbed onto single wall carbon
Consequently, only a few computational approaches have been applied nanotubes (SWCNTs). The results show that the adsorption of glucose
for the investigation of bioelectrochemical systems. These computa­ oxidase onto SWCNTs affects the structural change of the coenzyme
tional approaches include static density functional theory (DFT), mo­ [29]. Later, a similar study has been reported by the same authors
lecular dynamics (MD) simulations, computational fluid dynamics including explicit solvent water molecules [30]. The TIP3 water model
(CFD), artificial intelligence or artificial neural networks (ANNs), and has been used to fill the boxes for solvation in water [30]. Furthermore,
quantum mechanics/molecular mechanics (QM/MM) simulations molecular dynamics simulations have been performed by Graf et al. [31]
(Fig. 2). Exploration of the literature shows that very few studies have to determine the hydration free energies of thirty two aldohexopyra­
been reported using DFT and MD simulations. Most of the investigations noses (stereoisomers). They have also calculated the binding free en­
have been performed using the computational fluid dynamics. In this ergies between pyranose dehydrogenase (PDH) and the thirty two
section, we highlight some important results reported on BESs using stereoisomers. The PDH is a good candidate catalyst for application in
computational approaches. BES systems. The MD simulations have been performed using the 53A6
force field, and the SPC water model [31]. The investigation has pro­
vided a relationship between substrate promiscuity in PDH and the
3.1. Density functional theory (DFT) calculated binding free energies. These results are important for appli­
cations in bioelectrochemistry, and open a route for further studies using
Density functional theory (DFT) was used in some studies on BESs. the proposed computational approach [31].
These studies were mainly performed to provide complementary infor­
mation to experiments conducted. Molecular simulations have been
3.3. Computational fluid dynamics (CFD)
performed by Taninaka and co-workers to understand the conductance
pathways in a single-molecule junction [25]. The simulations have been
Several authors have used the computation fluid dynamics (CFD)
performed using local density approximation (LDA) and Perdew–Zunger
approach for investigations related to application in bioelectrochemistry
functional of DFT. Two systems have been studied and simulated: the 1,
[32–37]. The investigations using CFD mainly focused on the mass
transport in MFC. Several computational packages are used for the in­
vestigations, including Fluent, GAMBIT, COMSOL, and SimuL ink. Kim
et al. [32] have used CFD to study the mass transport of MFC along with
two electrodes. They have found that the flow is less uniform with LVSF
[32]. In addition, interaction of biological organism with electrodes
have been investigated through the flow of MFC [33]. The study has
been performed using the computational fluid dynamics simulated using
Fluent package [33]. Recently, Karimi and co-workers [37] have
developed a computational fluid dynamics model to simulate the mass
transfer in BESs. It is worth noting that CFD does not focus on the in­
dividual interactions of molecules with electrodes as done using DFT,
molecular dynamics and QM/MM approach described below. However,
Fig. 2. Summary of computational approaches used to study BESs. the CFD describe the flow of all the particles to understand their average

3
S. Ahmadi et al. Journal of Environmental Chemical Engineering 11 (2023) 110021

motion and impact. Table 1

biokinetic and kinetics models for emerging contaminants removal efficiency by
3.4. Artificial neural networks (artificial intelligence) BESs.
biokinetic EQ Parameters ref
Amongst the computational approaches used to study bio­ Michaelis- 1 ( K ) 1 1 (Ks) half-saturation
S
electrochemical systems, artificial neural networks or generally artificial = × + [15]
Menten V Vmax s Vmax concentration
intelligences are one of the most promising. Lesnik and Liu [38] have (Vmax) the maximum
used the artificial neural networks to predict the reactor performance of specific biodegradation rate
Grau model HRT /E = a+Bhrt - substrate concentrations of
thirty three MFCs. Data were split into test and training datasets to the ( S )2 [53]
ds influent (S0) and effluent (Se)
evaluate the performance of the model. The authors have found that the − = K2 • X
e
(mg/L),
dt S0
built model has an error of 4.07 % on the removal rate [38]. the flow rate of wastewater Q
Back-propagation artificial neural network has been applied by Liu and (L/day), effective volume V
co-workers [39] to predict the production of CH4 molecules. The of reactor (L), (HRT)
hydraulic retention time
methane molecules are part of a bioelectrochemical system (Biogas (day), K1 - the first-order
produced from anaerobic digestion). The built model has the R2 corre­ substrate removal rate
lation coefficient of 0.99 on the training set while the R2 is found to be constant (1/d)
0.92 on the test set. This indicated a reliable machine based on ANN to Modified Stover- dS V saturation constant KB (mg/
( )− 1 = = [53]
Kincannon dt Q(S0 − Se) L⋅day), - maximum substrate
predict the production of CH4 [39]. Besides, some other works have ( )
model KB v 1 removal rate Umax (mg/
applied artificial intelligence for application in bioelectrochemical sys­ .
Umax QS0
+
Umax L⋅day),
tems [40]. first order (C )
t (t) - the reaction time. (K1) -
ln = − K1 t [54,
kinetic C0 the reaction rate constant
55]
3.5. Quantum mechanics/molecular mechanics (QM/MM) second order 1 1 the initial phenol
− = K2 t [54,
reaction Ct C0 concentration in the solution
The QM/MM approach is a combination of quantum mechanics and C0 (mg/L), the final phenol 56]

molecular mechanics. Within this model, a small part of the system concentration in the solution
Ct (mg/L). the reaction rate
where the interactions occur are treated quantum mechanically while
constant K2
molecular mechanics is applied to the remaining of the system. The QM/ Haldane’s μmax.maxS - the inhibition constant Ki, -
MM approach has been applied to study bioelectrochemical systems by
μ =
S2 [54,
inhibitory Ks + S + ( ) the half saturation constant
K1 57]
few authors. Using QM/MM approach scientists have been interested by growth Ks maximum of growth rate
proton and electron transfer between the bioelectrochemical system and kinetics μmax, the substrate S.
The yield coefficient (Y) f
the electrodes [41,42]. The proton and electron transfer are studied Edwards ( s )
r: output voltage which can
using the Marcus theory [43]. The reported results have been found to r = rmax [exp − − [48]
Ki be obtained (mV), rmax:
be important for application in bioelectrochemistry especially to
)]
( s maximum output voltage
exp −
enhance the efficiency of enzymatic fuel cells design. As can be seen Ks which can be obtained (mV),
Ki: dissociation constant for
above, different computational approaches have been applied to un­
inhibitory substrate-enzyme
derstand part of the whole process involved in the application of bio­ interactions (g/L), S:
electrochemical systems. Investigations at molecular levels, especially substrate concentration (g/
using quantum mechanics are limited to few hundreds to a thousand L).
atoms. Although quantum mechanics is the most appropriate approach Luong rmax S(1 − S/Sm )n Sm: critical inhibitory
r = [48]
Ks + S concentration above which
for full understand of process at molecular level, its implementation in the reaction stops (g/L).
BESs remains complicated due to huge number of atoms involved. Hans- S n
rmax S(1 − [48]
Consequently, most of the studies have been performed using the
)
Levenspiel Sm
r =
computational fluid dynamics or classical molecular dynamics. S + Ks (1 − S/Sm )n
Moser Sn
μ = μmax [49]
Ks + S n
4. Biokinetic and kinetic studies

Currently, there are only a few papers dealing with the kinetics and for oil degradation from wastewater (R2 = 0.84). There were much
biokinetics of BESs, which we will review in this section. To optimize better predictions for BER used for oily wastewater treatment when
biological processes, kinetic models are an important step in predicting Grau Second-order and Stover-Kincannon models were applied [205] as
and controlling design of bioreactors [44]. Various biokinetic and ki­ depicted by R2-statistics of 0.96 and 0.97, respectively. For oily waste­
netic models in biodegradation have been used in the articles. Common water treatment the application of BES with electrostimulation was
microbial growth kinetics models used in BESs include linearized much more efficient as modeled using Michaelis-Menten kinetic model
Michaelis-Menten, modified Gompertz model, Monod [45], Haldane (R2 = 0.9955). MFC bioreactors seemed to be much more appropriate
[46], Tessier [47], Edwards [48], Luong [48], Hans-Levenspiel [48], for degradation of emerging pollutants (both organic and inorganic) as
Moser [49], Blackman [50], Monod–Nerst [51], Multiplicative Monod depicted with First-order kinetic, Michaelis-Menten and second order
[52], First-order kinetic model [53], Grau model [54], Modified models used (R2 = 0.98–0.99). One example of wastewater denitrifica­
Stover-Kincannon model [54], second order [55] and etc. (Table 1). tion was presented by Zhang and co-workers [200] using Han–Leven­
Determining the best model depends on the correlation coefficient (R2). spiel model with R2 of 0.98. Experiment showing the effect of very low
Monod and Monod-type kinetics are one of the most common kinetic alternating current on biodegradation of high concentration of aspirin,
models of microbial growth. In the study of Mirolieu [49] it was the specific Michaelis-Menten linear equation was used. The results
demonstrated that the Moser model in MFCs to predict the specific showed that the dose of 400 mg aspirin/L could be critical for biodeg­
growth was not very high (0.8) while when using Mond model the radation and R2 was 0.99 [15]. Similar results were obtained for peni­
estimated R2 was much higher (0.92). Typically, these models can only cillin when First-order kinetic model was applied (R2 = 0.98) [146].
describe or predict the performance of a biosystem in operations on the Therefore, according to the studies conducted, Michaelis-Menten model,
laboratory scale [44]. Similarly, the study of Mirshafiee and Rezaee First-order kinetic and second order models can be a suitable option for
[205] demonstrated low model prediction when BER bioreactor was use forecasting in BESs, particularly in MFCs (Table 2)

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S. Ahmadi et al. Journal of Environmental Chemical Engineering 11 (2023) 110021

Table 2
Summary of kinetic and biokinetic parameters in BESs.
Pollutant Form Type of BES Concentration kinetic Model Parameter R2 ref
(mg L− 1)

methyl orange MO MFCs - PFO k1 = 0.279 ± 0.005 h− 1 0.989 [58]

oil - biofilm-electrode reactor (BER). COD: 1500 PFO K1 = 0.485 h− 1 0.847 [53]
RB5 RB5 - PFO K1 = 0.146 ± 0.008 h− 1 0.987 [59]
1
As(III As MFC PFO K1 = 0.06532 ± 0.0005 h− 0.934 [60]
(III)
Penicillin PC MFC 50 PFO K1 = 0.167 h− 1 0.98 [61]
tetracycline TC MFC 50 PFO K1 = 0.060 h− 1 0.99 [62]
Orange G OG two-chamber MFC - second-order K1 = 543.10 0.9827 [63]
acid orange 7 AO7 MFC PFO K1 = 0.709 0.05 h− 1 0.994 [64]
aspirin A bench-scale bioreactor 400 Michaelis-Menten - Vmax: 0.83 g / g− 1 0.99 [15]
Ks: 34.82 / L− 1
oily - BER COD: 1500 Second-order b (dimensionless)= 0.694 0.961 [53]
wastewater (Grau)
oily - BER. COD: 1500 Stover-Kincannon KB (g/L⋅d)= 0.767 0.975 [53]
wastewater Umax (g/L⋅d)= 1.106
Biofilms - Alternating electric current on bioelectrical - Michaelis- Vmax and Ks:3.13 g \d and 5.99 g/ 0.972 [65]
reactor biofilm Menten mode L
oily - BES 1100 Michaelis–Menten Vmax and Ks: 0.44 g / g and 0.9955 [66]
wastewater 90.31 g/L
methylene MB MFC - Moser - 0.8 [49]
blue
methylene MB MFC Monod - 0.92 [49]
blue
nitrate NO3 AD-MFC 1999.95 Han–Levenspiel Ks (mg/L)= 351.63 0.984 [48]
± 2.86

5. Predominant microorganisms for EPs degradation aromatic hydrocarbons and pesticides [81]. Similarly, in other studies,
Rhodococcus strain has been observed to help in the degradation of
In this section, we examine the predominant microorganisms as well pharmaceutical compounds [82], tetrabromobisphenol A [83] and
as the microbial metabolism in degradation of emerging pollutants naphthalene [84],while Streptococcus strain has been observed in the
(EPs). Electroactive microbes present in the anodic chamber of BESs removal of Carbamazepine [85,86]. These microbes constitute the
acting as biocatalyst, play pivotal role in bio-electrochemical degrada­ electrogenic microbial consortia for a typical MFC that aids in the
tion through oxidation of EPs (antibiotics, estrogens, heavy metals, degradation of the complex organic complexes [87]. Notably, it has been
phenols, dyes, surfactants, and others), that even at lower concentration found that the bacterial genera of Chryseobacterium, Stenotrophomonas,
proves to be hazardous to the environment [67]. Additionally, the mi­ Arcobacter, and Comamonas are predominantly present in the anodic
crobial metabolisms and electrochemical redox reactions in BESs are biofilm of the MFC [87].
recognized as critical means for this degradation [68]. During degra­ The bio-electrochemical degradation of these EPs depends largely on
dation of EPs by electrogenic microbial consortia electrons generated several parameters [88–91] including: flow rate, additives, source of
are conveyed between electrodes using external circuit what leads to the inoculation, type of anolytes (acetate or glucose) for improving micro­
production of electricity [69]. The inoculation of the anode chamber of bial diversity, pH, and buffer solution [92–94], electrochemical prop­
BESs can be performed by pure and mixed culture. Pure cultures are erties and initial concentrations of EPs, electrode material and applied
beneficial because they eliminate EPs such as pharmaceuticals and potential, carbon source, temperature and salinity [68].
phenols. On the other hand mixed cultures are also implemented to treat High-throughput sequencing has permitted to explore the key micro­
industrial wastewater polluted with varied organics [70,71]. Notably, organisms and to comprehend the shifts in the microbial communities
the microbial electroactive growth and diversity at the anode chamber with these indicated parameters [68]. For instance, studies have shown
upset the startup time of BESs. Therefore, it is of prime importance in that the electrochemical properties of the target EPs in the BESs are one
improving and maintaining the diversity of these microbes by adopting of the significant limitations allowing to decide if the BESs anode or
strategies such as the recycling of effluent in anodic chamber or a use cathode are suitable for their elimination [95]. Similarly, more negative
selected pure culture with anaerobic inoculum [72]. Despite aerobic and applied potential enhances the removal of EPs and sharply shortens the
anaerobic degradation of complex organic substances, it has been noted hydraulic retention time (HRT) of biocathodes [96,97]. Electrode
that the degradation rates of these complex organic substances are quality is also very crucial for the overarching performance of the BESs
higher under aerobic conditions [73,74]. The microorganisms produc­ because microorganisms spread over the electrode as biocatalysts
ing bioelectricity are termed as: electroactive [75,76], forming biofilms for electron transfer [98,99]. Furthermore, the carbon
electricity-producing [77], electrogenic [78], exoelectrogens [79] or source plays a significant role between competition and commensalism
electricity-generating [80]. Predominantly microbes belonging to the of the electroactive, electricigenic anode respiring and electrogenic
phyla Proteabacteria, Firmicutes and Bacteroidetes are found in most of microbial bacterial community and its metabolism [100,101]. Both high
the BESs reactors. For instance, a previous study has revealed the salinity [102–104] and temperature [95,105,106] affect the bacterial
presence of Firmicutes followed by the Actinobacteria, predominantly growth that influences the biological activities and conductivity of
involved in the aerobic degradation of the EPs such as Galaxoxide, wastewater that involves redox reaction rates in BESs [68].
Padimate O, Carbamazepine, Tonalide and Octocrylen. Among the Fir­
micutes, only the Bacillus-related strains have been isolated, while the 6. Microbial metabolism in degradation of EPs
Actinobacteria has been observed to be dominated by Rhodococcus >
Streptococcus > Mycobacterium > Micrococcus [74]. In another study, The MFC of the BESs is grounded on the transformation of chemical
Bacillus strains, such as Bacillus thuringenesis isolated from the marine energy into electrical energy using electrogenic microbes [87]. A typical
sediment has been observed to be involved in the removal of polycyclic MFC system is operated by two electrodes, namely, biological anode and

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S. Ahmadi et al. Journal of Environmental Chemical Engineering 11 (2023) 110021

abiotic cathode disconnected internally by proton exchange membrane membranes and travel to anode where electron acceptors are present. As
(PEM). In the anode compartment, the electrochemically active bacteria produced electrons need to be balanced the equal number of protons is
(EABs) oxidize the organic substances present in wastewater to CO2, transmitted via circuit [113]. The e-gathered by anode travel through
resulting in the generation of electron (e-), and proton (H+). Typically, external conducting wire into the cathodic chamber, where they reduce
organic matter(OM) in wastewater oxidize by anaerobic bacteria and electron receptors (oxygen, nitrate, and metal ions) at the cathode.
product carbon dioxide that it using the anode as the final electron Microbial decomposition of OM produces also protons and hydroxyl ions
acceptor. (OH-) in cathodic reactions [114]. Protons in cathodic chamber com­
The anodic oxidation reaction is conveyed by the decomposition of bines with oxygen forming water molecule [115–117] (Fig. 3). Notably,
acetate or glucose [107]. Microbial anaerobic respiration of OM releases the PEM, although permeable to H+ acts as a barrier to restrict the
electrons at a higher potential further are transferred to the anode. substrate, oxygen diffusion from cathode to the anode as well as limit
Electrons are transferred by microorganisms to a solid electron receptor electrons not to cross over [117,118]. The exoelectrogenic bacteria form
(anode) located outside the cells using extracellular electron transfer the biofilms on the anodic surface and oxidize the EPs [94]. The
mechanisms (direct transfer methods, electron shuttles, biofilm oxidation of the EPs and their metabolites involve the release of elec­
matrices, cells) for their movement to a solid electron receptor (anode) trons that provides an electrical stimulation to the microbes that in turn
located outside the cells, which are the way for the anaerobic bacteria to stimulate the microbial metabolism, which is a crucial step that decides
gather energy for their growth [2]. In the anode chamber microorgan­ the successful degradation of these EPs in the BESs [94]. The survival
isms use existing substrates to produce ATP (adenosine-5-triphosphate) tactics of microorganisms is their capability to transfer the electrons to
which is an energy-carrying molecule. Organic matter is converted to interspecies [75,119,120], natural metals [121] including electrodes
citric acid by glycolysis, further to carbon dioxide while electron carries [122]. The transfer of electrons between various bacterial species from
such as NAD+ (nicotinamide adenine dinucleotide) and FAD+ (flavin different phyla is a way to regulate their metabolic process [122–124]
adenine dinucleotide) are also reduced to NADH and FADH2, respec­ and allows external communication [125] between microorganisms
tively [108,109]. Electrons are conveyed from the cell cytoplasm (the [126]. OM of EPs is metabolized by enzymes secreted by stimulated
citric acid cycle) to membranes and next to the anode through direct microorganisms. For instance, the degradation of Sodium Dodecyl Sul­
electron transfer mechanisms or mediators [110]. Therefore, the anode phate (SDS) at the anodic chamber of the BESs is done by the desul­
plays a pivotal role as an external electron receptor and in the oxidation phurization of long alkyl chain of SDS. The alkyl sulphatase, enzyme
of the organic substrate. Bacteria present at biocathodes transfer elec­ identified in Pseudomonas aeruginosa, P. putida and P. otitidis, breaks
trons(biocatalysis) substituting chemical catalysts [111]. Oxygen, ni­ down the sulfate esters and metabolize the SDS [127,128]. Similarly,
trates, and chlorinated organic compounds (high electro-positivite SMX antibiotic can be degraded by microbial secreting enzymes into its
electron receptors) aid in electron transport through the cells inner and by-product 3-amino-5-methylisoxazole [94]. Likewise, Citrobacter sp.
outer membranes and periplasm [112]. The ability of mircroorganisms has also been noted to degrade anionic surfactant [129]. Other Pseu­
for easy electron transport and energy storing is confirmed by high domonas sp. along with Geobacter and Shewanella have been observed as
standard redox potential (E◦ ). To summarize electron transfer between the most abundant in the MFCs, responsible for the degradation of 97 %
two electrodes mediated by microorganisms is related to OM degrada­ of phenol from wastewater(concentration of 100 mg/L, operation time
tion [1]. Organic matter is decomposed to low molecular organic acids of 48 h) [130]. A study have also shown that Treponema sp. (Clos­
which is accompanied by electron release which are transferred to ac­ tridiaceae) isolated from the sulphate-rich sediments/soil appeared as
ceptors such as oxidized inorganic compounds. Reduced organic com­ electrogens being responsible for the degradation of EPs, such as sulfa­
pounds are metabolized via Krebs cycle resulting in energy storing in a methoxazole, which is a pharmaceutically active compound [130].
form of ATP by microorganisms. Electrons moves through cell Notably, the EPs can also be directly degraded by accepting the e- from

Fig. 3. Schematic representation of the underlying mechanisms for the BESs. Microbes plays the pivotal role in driving the BESs.

6
S. Ahmadi et al. Journal of Environmental Chemical Engineering 11 (2023) 110021

the cathode by the electrochemical reduction. Additionally, the mi­ requirement for hydrogen production in MECs [141]. The performance
crobes at the cathode chamber can also reduce lower overpotential, of this process is however hampered at pH < 3 as the resulting acidic
thereby facilitating EPs elimination [94]. On the other hand, the direct conditions are no longer appropriate for most electrogenic microor­
electron transfer (DET) involves direct physical contact between a bac­ ganisms [138,142].
terial cell membrane enzymes (inner membrane, cytochrome type C and
periplasm) and the electrode surface that transfer the electrons from the
7.2. Effect of temperature
bacteria to the electrode [126,131]. Certain electrochemically active
bacteria from Shewanella, Rhodoferax and Geobacter genera, capable of
Temperature is another important factor for functioning of BESs
producing pili or conductive nano wires that help bacteria to attach to
[138]. Temperature affects COD removal in these reactors, power gen­
the electrode, even at a distance of 40–50 µm from the electrode surface
eration in MFCs, and hydrogen production in MECs [143] lowering the
[126,132]. Concurrently, the membrane bound electrons transfer pro­
flow of electrons form the anode to the cathode. In general, high tem­
tein also facilitate the transfer of the electrons from the bacterial cell to
peratures (>45 ◦ C) are important in the described changes [144]. Most
its outer surface (the electrode) or vice versa, however the rate of this
studies showed that higher temperature increases the output power in
transfer is comparatively slow due to the minimal exposure of the en­
BESs. The structure, level and activity of microbial enzymes is disrupted
zyme’s active site to the electrode. Notably, some redox enzymes of
when the temperature reaches a certain value, reducing the performance
exo-electrogenic bacteria are located on the outer membrane, easing the
of BESs [145]. Higher temperatures may increase mass transfer effi­
electron transfer as the active sites of these redox enzymes are in
ciency [138]. On the contrary, at low temperatures, the growth of
direct/close contact with the electrodes [126,133]. Lastly, multi-layer
methanogenic bacteria is inhibited and helps to produce hydrogen. It
electroactive biofilms can also be formed on the electrodes, resulting
was documented that the variation of temperature on MEC affected the
in increased bio-electrode performance [126,134]. According to Table 3,
number of methanogens lowering their number by 68–91 % at 4–9 ◦ C
the performance of BESs in reducing wastewater metals reaches more
[2,146]. But the increase of abundance of methanogens and their cor­
than 90 %. No, applications of the BES system have seen a significant
responding re-establishing of the activity were noted when the tem­
expansion in the reduction of metals from wastewater[135,136]. Fig. 4
perature rose to 30 ◦ C [138].
depicts the mechanism of heavy metals removal in the selected BESs in
the cathode chamber[136]. In summary, the application of BESs gen­
erates green energy that can be implemented for a range of purposes 7.3. Anode material and its available surface
such as remediation of environmental compartments, agriculture,
landscaping, greenhouse gases mitigation, and powering of electrical The surface characteristics of electrodes and the available surface
devices. area for bacteria, which depend on the nature, material and shape of the
electrode, are two effective factors in biofilm formation and the effi­
7. Factors affecting in Bioelectrochemical systems (BESs) ciency of bioelectrodes [138]. Increasing the size of bioelectrodes to
perform the reduction-oxidation reaction increases the electron transfer
Various contaminants such as nitric acid, nitrobenzene, nitro- rate [147]. Bacteria that are able to exchange electrons with electrodes
aromatic perchlorate, pesticides, dyes, aromatic hydrocarbons, oils, easily attach to their surface and easily transfer electrons what stimu­
and heavy metals that they call emerging pollutants (EPs) can removed lates their metabolism. The electrode should be made of a high perfor­
by BESs (Table3). Many reactions occurring at the electrode surface can mance electrocatalyst material [148]. For this purpose, different
affect the behavior of microorganisms but the interactions between materials as electrodes have been tested. The use of platinum anodes
microorganisms and the active electrode remain unknown. For this have been successfully demonstrated for removing organic contami­
reason, this review describes key factors important during for waste­ nants but their usage can lead to high initial investment costs of the
water treatment using BESs. Below sections describe the factors which process [149]. The mostly widely material used as anode is stainless
can affect the system performance. As in some reviewed articles the steel, its good performance in reducing the organic pollutants have been
factors affecting microbial activity are mentioned we decided only to reported [150]. Carbon structures have diverse variations and applica­
mention them briefly also mention new factors affecting [2]. tions in chemistry due to the specific chemistry of carbon atoms. The key
factors that make the use carbon for these purposes are the availability
7.1. Effect of pH of this material, low price, easy processing, the ability to create different
shapes (powder, fibers, foam, woven fabrics and composites) [151]; the
One of the important parameters affecting microbial activity is pH of porosity is adjustable and its surface is functional. Carbon electrodes are
the substate [9] showing optimum of 6–7 for their grow [137]. The stable in acidic, basic and proton-free solutions and are also stable over a
microorganisms present in the anodic chamber convert the energy of wide range of temperatures [7]. The amphoteric nature of carbon ma­
chemical bonds of the substrate into electrical energy by using the terials and the simultaneous presence of alkali/acid surface groups
electrons obtained from the oxidation of the substrate [10]. As a result of create various electrochemical properties of carbon-based materials [2].
their activity (indicated as the removal of COD) the pH value of the The efficient oxidation of OM and direct electron transfer were
anodic chamber increases [138]. In other words, the removal of COD demonstrated in the presence of bacterial biofilms formed on graphite
and the substrate affect the pH of the anodic chamber [11]. During [59]. Some electrodes modifications were demonstrated - graphite an­
anodic oxidation of organic matter (OM), the pH value in the anodic odes were coated with electron mediators, active polymers, polyaniline
chamber decreases [138]. Some researchers have found pH buffering by and quinone groups [84]. By increasing available surface area of the
carbonate buffer [84] and thus affecting the bacteria [139]. pH is also electrode more available space for the bacteria was obtained, thus
very crucial for microbial activity at cathode [138]. The removal of COD increasing the rate/speed of electron transfer [152]. Obviously, this is
in BESs depends on pH of a substrate; it can be nearly 3 times higher at true in a situation where the resulting force and the production of
extreme pH [138]. As a result, the microbial activity in MFCs, and MECs electricity depend on the biofilm present on the electrode [2]. In the
is lower at suboptimal pH as compared to optimal values. This is related study of Li et al. [140] the reduction of 80 mg Cr (VI)/L from synthetic
to the altered proton transfer through the proton exchange membrane wastewater was demonstrated for carbon felt anode and three different
(PEM). Under pH above 10 microbial activities become lower due to types of cathode materials separately (carbon cloth, brush and felt).
decreased proton concentration gradient [97,138,140]. At low pH pro­ Using a conventional MFC system under pH 1–7, the reduction efficiency
ton gradient is accelerated increasing their availably in the cathode of metals was estimated to be 100 %, 33.45 % and 12.72 %, respectively
chamber allowing biohydrogen production resulting in lower pH [140]. More electrons were received when As was used (Table 3).

7
 S. Ahmadi et al.
Table 3
Summary of kinetic and biokinetic parameters in BESs.
Pollutant Form BES type Inoculation Concentration HRT Temp pH Characterizations RE ( %) End-products Ref
(mg L− 1) (h) (◦C)

Mercury Hg2+ macrophyte Sediment MFC wastewater 0.62 ± 0.04 288 - 6.8 SEM 95.78 Hg0 [135]
(mSMFC)
3+
Arsenic As mSMFC wastewater 0.08 ± 0.03 288 - 6.8 SEM 89.18 AsH3 [135]
Palladium Pd2+ mSMFC wastewater 0.32 ± 0.06 288 - 6.8 SEM 99.58 Pd0 [135]
Zinc Zn2+ Dual-chambered (DC-MEC) Sediment 15–25 96 30 3 - 99 ZnS, Zn(OH)₂ [167]
Cadmium Cd2+ DC-MFC activated sludge 8–50 24 35 - SEM,XPS,FTIR 95 Cd(OH)2 [168]
Arsenic As(III) single-chamber MFC activated sludge 2000 - 22 ± 2 - - 84 AsO4−3 [169]
Chromium Cr(VI) DC-MFC Wastewater containing 250 240 30 7 XPS,SEM,EDX 75.4 Cr(OH)3, Cr3 + [157]
chromium
Gold Au(III) DC-MFC Tetrachloroaurate 200 3 25 ± 1 2 - 99.89 AuCl-4,Au0 [170]
wastewater
Cobalt Co(II DC-MEC Cobalt solution - 6 25 6.2 XRD,EDS,SEM 92.2 Co0 [142]
Cadmium Cd(II) DC-MEC Acetate or NaHCO3 50 - 25 - XRD,EDSSEM 88 Cd [171]
solution with Cadmium
Silver Ag(I) DC-MFC Silver sulphate and silver 500 36 - 10 SEM,EDX 95 Ag0,Ag2O [172]
nitrate solution
Zinc Zn(II) MFC–SLM hybrid Zinc wastewater 200 72 - 9.2 - 93 ZnR2 [173]
three-compartment
Boron B(III Tubular reactor with one layer of NaCl and boric acid 5 8 - 10.6 - 90 BOH−4 ,BOH3 [174]
AEM solution
Copper Cu(II) DC-MFC CuCl2 solution 350 12 35 9 SEM,XRD, 96 CuNH23 [152]
Cu2O, Cu
Copper Cu(II) Tubular dual-compartment CuSO4 solution 50 78 30 3 SEM,EDX > 99 Cu0 [175]
Chromium Cr(VI) Coupled MFC–MEC Chromium, copper and 50 - 20 ± 3 - EDX, 56.4 Cr(OH)3 [176]
system cadmium solution XRD
8

Vanadium V(V) DC-MFC Vanadium containing 150 12 25 ± 2 2 XPS,SEM,EDX 76.8 VO2+,V4 + [177]
wastewater
Nickel Ni(II) DC-MEC Artificial AMD 530 62 25 7 SEM,XRD 97 Ni0 [178]
Arsenite As(III) DC-MFC PBS with As(III) solution 0.1 30 30 7 FT-IR > 95 As( V) [60]
Chromium Cr(VI) DC-MFC K2Cr2O7 solution 100 48 20 ± 2 7 XRD, 100 Cr2O3 [179]
FTIR
Cobalt Co(II DC-MFC Nutrient medium with 20 20 ± 2 5.6 XRD,XPS 90 CoðOHÞ2 [180]
CoCl2
Silver Ag(I) DC-MFC Silver nitrate 1000 0.17 7 - 99 Ag0 [181]

Journal of Environmental Chemical Engineering 11 (2023) 110021

Mercury Hg(II) DC-MFC Artificial wastewater nutrient 100 0.25 30 2 - 99.54 Hg2+
2 , Hg, Hg2Cl2 [182]
Chromium Cr(VI) DC-MFC - 200 20 25 - XPS,SEM,EDX 100 Cr(OH)3, Cr3+ [183]
chloramphenicol CAP two-chamber MEC bioelectrochemical reactor 32 24 - 6 LC–MS 100 CO2, H2 O [184]
effluent
cefazolin sodium CFZS air-cathode single-chambered MFC aerobic activated sludge 50 31 - 7 SEM > 70 CO2, H2O, Electricity [185]
chloramphenicol CAP biocathode with anaerobic sludge 50 72 25 ± 1 - - > 90 CO2, H2O, Electricity [186]
chloramphenicol CAP biocathode with anaerobic sludge from a 30 72 25 7 - 92.50 CO2, H2O [186]
bioreactor
metronidazole MNZ two-chamber MFC anaerobic sludge 10 24 30 ± 1 7 SEM 85.4 CO2, H2O, Electricity [187]
nitrofurazone NFZ biocathode with nitrofurazone- reducing 50 1 23 ± 3 - 70.60 CO2, H2O [188]
consortium ± 4.21
penicillin - air–cathode single-chambered another MFC in group 50 24 24 ± 2 6–7 - 98 CO2, H2O [61]
ceftriaxone sodium CFZS air–cathode single-chambered MFC another MFC in group 50 24 24 ± 1 7 - 91 CO2, H2O, Electricity [189]
tetracycline TC three-dimensional biofilm-electrode anaerobic sludge 0.2 40 28 ± 2 - - 89.3–95.6 CO2, H2O [190]
reactors
tetracycline TC three-dimensional biofilm-electrode anaerobic sludge 0.2 40 28 ± 2 - - 82.61–95.80 CO2, H2O [191]
reactors
tetracycline TC MFC coupled with photo- N.M 100 2 - - SEM 70 CO2, H2O, Electricity [192]
electrochemical catalysis
(continued on next page)
 S. Ahmadi et al.
Table 3 (continued )
Pollutant Form BES type Inoculation Concentration HRT Temp pH Characterizations RE ( %) End-products Ref
(mg L− 1) (h) (◦C)

chloramphenicol biocathode with activated sludge 30 24 30 - - 86.3 CO2, H2O [193]

chloramphenicol biocathode with activated sludge 32 24 26 ± 2 - SEM and EDX 96.0 ± 0.9 CO2, H2O [194]
tetracycline TC MFC coupled with membrane Shewanella sp. 90 17 - - - 99.5 CO2, H2O, Electricity [195]
bioreactor
tetracycline TC two-chamber MFC Anaerobic activated sludge 50 168 20 7 - 79.1 CO2, H2O [196]
tetracycline TC two-chamber MFC pig manure 10 78 25 7 - 99 CO2, H2O, Electricity [177]
sulfamethoxazole SMX two-chamber MFC anaerobic sludge 20 48 35 ± 2 7 SEM > 99 CO2, H2O, [197]
sulfamethoxazole SMX two-chamber MFC sulfamethoxazole 48 30 ± 1 7 - 83.3 CO2, H2O [198]
acclimatized culture
sulfamethoxazole SMX two-chamber MEC municipal wastewater 0.006 168 30 - - 100 CO2, H2O [199]
chloramphenicol CAP biocathode with anaerobic sludge 30 48 30 ± 1 7 - 83.7 CO2, H2O, Electricity [200]
chloramphenicol CAP two-chamber MFC anaerobic sludge 50 12 37 7 - 84 CO2, H2O, Electricity [201]
sulfanilamide SMX two-chamber MFC anaerobic sludge 30 96 7 - 90 CO2, H2O, Electricity [202]
sulfamethoxazole SMX MFC coupled with constructed anaerobic sludge 60 28 ± 2 - - > 99 CO2, H2O, (
wetlands [190]
Active brilliant ABRX3 Air-cathode single-chamber Dyeing Chemical 100 24 30 ± 1 - UV–visible 90 CO2 and H2O [203]
redX-3B Industry
Acid orange 7 AO7 DC-MFC Anaerobic sludge 35 30 30 7 UV–visible 98 Sulfanilic acid,1-amino-2- [64]
naphthol
Congo Red CR DC-MFC anaerobic sludge 4000 14.8 35 - UV–vis spectra 92.7 CO2 and H2O [159]
Reactive yellow 145 RY145 air-cathode MFCs Activated sludge of Bakery’s 40–80 24 30 ± 2 7 - 92 ± 2 CO2 and H2O [204]
wastewater
Reactive red 195 RR195 air-cathode MFCs Bakery’s wastewater 40–80 24 30 ± 2 7 - 74 ± 2 CO2 and H2O [204]
Remazol black RL RB air-cathode MFCs Bakery’s wastewater 40–80 24 30 ± 2 7 - 78 ± 11 CO2 and H2O (
[204]
Remazol turquoise RTB air-cathode MFCs Bakery’s wastewater 40–80 24 30 ± 2 7 - 53 ± 5 CO2 and H2O [204]
9

blue
Remazol brilliant RBB air-cathode MFCs Bakery’s wastewater 40–80 24 30 ± 2 7 - 94 ± 1 CO2 and H2O [204]
blue
Dye wastewater - a granular activated carbon based Aerobic sludge and dye 488 48 - 7–12 - 73 CO2 and H2O [205]
MFC (GACB-MFC) wastewater
Dye wastewater - GACB-MFC Dye wastewater 488 48 - 7–12 - 77 CO2 and H2O [205]
Reactive blue 221 RB221 DC-MFC diary wastewater treatment 112.5 - 28 ± 1 7 - 87 CO2 and H2O [206]
Amaranth AG - MFC-Fenton 75 1 20 3 - 83 CO2 and H2O [207]
Orange G OG DC-MFC Dye wastewater 45 12 30 3 - 97.4 CO2 and H2O [63]

Journal of Environmental Chemical Engineering 11 (2023) 110021

Active brilliant red ABRX3 CW–MFC Anaerobic sludge 150 72 25 ± 2 - - 91.24 CO2 and H2O [208]
X-3B
Reactive blue 198 RB198 Single chamber air Proteus hauseri ZMd44 450–560 480 30 - - 14.4 CO2 and H2O [209]
Reactive red 198 RR198 Single chamber air Proteus hauseri ZMd44 450–560 480 30 - - 98.8 CO2 and H2O [209]
Acid yellow 42 AY42 Single chamber air Proteus hauseri ZMd44 450–560 480 30 - - 0 CO2 and H2O [209]
Reactive blue 171 RB171 Single chamber air Proteus hauseri ZMd44 450–560 480 30 - - 79.4 CO2 and H2O [209]
Reactive black 5 RB5 Single chamber air Proteus hauseri ZMd44 450–560 480 30 7 - 97.2 CO2 and H2O [209]
Reactive blue 160 RB160 Single chamber air Proteus hauseri ZMd44 450–560 480 30 7 - 97.2 CO2 and H2O [209]
Reactive green 19 RG19 Single chamber air Proteus hauseri ZMd44 450–560 480 30 - 89.2 CO2 and H2O [209]
Reactive red 141 RR141 Single chamber air Proteus hauseri ZMd44 450–560 480 30 7 - 92.7 CO2 and H2O [209]
Reactive yellow RY84 Single chamber air Proteus hauseri ZMd44 450–560 480 30 - - 75.3 CO2 and H2O [209]
Methyl orange MO MFC Synthetic 17.5 18 30 3 - 91 1-Amino-4 naphthol,Sulfanilic [210]
acid
Acid orange 7 AO7 MFCs A mixture of aerobic 50 1 30 ± 1 3 UV–visible 91 Sulfanilic acid,1-amino-2- [211]
naphthol,phenol, benzaldehyde,
naphthalene,CO2and H2O
Congo red CR Air-cathode single-chamber MFC anaerobic sludge 300 36 h 40 7 UV–Visible 98 [212]
Nitrobenzene (NB) A mixture of aerobic and 50 24 30 ± 1 - - 100 % - [159]
anaerobic sludge
(continued on next page)
S. Ahmadi et al. Journal of Environmental Chemical Engineering 11 (2023) 110021

[213]

[214]

[215]

[216]

[217]

[161]
[17]

[15]
Ref
End-products

CO2, H2O

CO2, H2O

CO2, H2O

CO2, H2O
CO2, H2O

CO2, H2O

CO2, H2O
-
RE ( %)

95.5

99.9

96.2

95.7
100

82

99

95

Fig. 4. Reduction process of metals in the cathode chamber of MFC, MEC,

and MES.
Characterizations

7.4. Effect of substrate concentration

The availability substrate (organic matter) affects both the pool of

-

bacteria and the morphology of their biofilm. Moreover, density of

produced electric current is affected too. Although higher initial con­
7.3

7.2
pH

centrations of OM stimulate its removal, they also reduce Columbic ef­

7

7
7

7
-

ficiency as organic matter is degraded in fermentation and

30 ± 1

23 ± 1

24 ± 1
25 ± 2

26 ± 1

methanogenesis becoming the by-product of these processes [7]. Under

Temp
(◦C)

20

constant conditions in terms of flow intensity when the initial concen­

◦

tration of organic matter increases its removal efficiency decreases [2].

HRT

6.5

6.5

At a constant electrical conductivity and voltage a certain amount of

(h)

12

60

12
2
2

hydroxyl radicals are generated by an electric current in the medium

Concentration

which may be adsorbed and it may participate in OM decomposition [3].

(mg L− 1)

7.5. The electrostimulation of bacteria

200

400

600

600

100
100

100

100

The role and effect of electric currents and fields on cell growth and
development demonstrated that the electric field can stimulate DNA and
Mixed aerobic and anaerobic

pharmaceuticals wastewater

pharmaceuticals wastewater
Synthetic pharmaceuticals

Synthetic pharmaceuticals

accelerate electron transfer. When electron reaches the paired bases in

A mixture of aerobic and

the DNA molecule, the conditions are created for the DNA strands to be
opened, which in turn provide the synthesis of biopolymers, enzymes, or
anaerobic sludge

cell growth [153]. Application of an electric field to the microbial sys­

Inoculation

wastewater

wastewater
wastewater
wastewater

tem was proved to increase the permeability of the cytoplasmic mem­

brane [154] allowing neutrinos to penetrate it [17]. Increased
sludge

permeability can also lead to leakage of the cellular content and extra­
cellular glycoproteins from bacterial cells and stimulate the ATP syn­
thesis [155]. Elevated electric field can also affect the activation of
single-chamber Plexiglas cylindrical

electron carrier species such as Fe2+/Fe3+ and H+ what directly affects

bioelectrical reactor(ACBER)

the ATP as enzyme, thereby promoting bacterial metabolism [156]. The

A ferricyanide-cathode MFC

alternating electric current

Biofilm electrode reactor

concentration of ATP in bioelectrochemical systems is approximately

A bench-scale bioreactor
double chamber MFC

1.5 times higher than that of conventional systems, and this amount of
bioelectrochemical
single-chambered

activity and metabolism in most microorganisms is attributed to elec­

trical stimulation [156]. In the evaluating the effect of electric current
on Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginus
BES type

reactor
system

[157] bacteria were exposed to electric current with sinusoidal wave­

MES

form conditions of 5 and 20 mA for 30 min. The results showed the

growth inhibition of E. coli during the whole study [158]. In other study,
the performance of bacterial denitrification (Pseudomonas denitrifica­
Form

tion) under a constant electric field in wastewater was investigated

[159]. Based on the results of applying a constant electric field to the
Table 3 (continued )

culture medium of denitrifies nitrate reduction was faster than the

classical denitrification, due to the lack of a long delay phase, and the
process rate and specific microbial activities were sensitive to the
Ibuprofen

Ibuprofen
Pollutant

cathode constant potential [160].

Furfural

Phenol

phenol
phenol

aspirin

aspirin

Microbial electrical stimulation can be performed in two ways,

including the use of direct current (DC) and alternating current (AC)

10
S. Ahmadi et al. Journal of Environmental Chemical Engineering 11 (2023) 110021

[161]. Most bioelectrochemical systems use direct current (DC) to sup­ study the efficiency of designed BESs what may help optimize their
ply the system with electricity. For example, in a study, using DC current functioning. As far as the computational studies are concerned, density
in the treatment of phenol-containing synthetic wastewater with a functional theory (DFT), molecular dynamics (MD) simulations,
conductive carbon electrode, the biodegradation of phenol under direct computational fluid dynamics (CFD), artificial intelligence or artificial
current was accelerated, and the effect of electrical stimulation was neural networks (ANNs), and quantum mechanics/molecular mechanics
directly related to the adenosine triphosphate content in the biofilm (QM/MM) simulations have been applied to the study of BESs. Although
[162]. Furthermore, the application of DC current intermittently with different computational approaches have been applied, exploration of
phenol removal efficiency (more than 97 %) [17]. Li et al. investigated the literature shows that most of the studies are performed using the
the excitatory effect of DC on the metabolism of Thiobacillus ferroxidans computation fluid dynamics technique. This orientation is understand­
in a bioelectric reactor without the cation membrane [144]. According able considering the size of BESs. Full investigation of BESs using
to them, at current intensity of 30 mA and time of 84 h the cell growth quantum mechanics (DFT) is almost intractable. Nevertheless, a com­
density was 10 times faster than their growth under normal culture bined quantum-classical approach (QM/MM) has been applied, which
conditions (without applying electricity). Furthermore, when applying should be the route to accurate understanding of processes involving
direct current with higher current intensity, a longer delay phase was BESs.
observed during growth [163].
AC current, unlike DC current and due to the nature of the cycle, has Declaration of Competing Interest
the ability to form a biofilm consisting of different types of bacteria on
both electrodes (anode and cathode) [17]. In AC bioelectrochemical The authors declare that they have no competing interests.
systems, bacterial activity can be changed by altering the current
characteristics, i.e. applied voltage, frequency and waveform. Sine wave Data Availability
is the closest waveform to the main nature of alternating current and is
generally one of the most acceptable waveforms [138]. During the pu­ No data was used for the research described in the article.
rification process, by applying alternating current at high frequencies,
the transfer of electrons can cause the ions to move periodically. How­ Acknowledgements
ever, the strength of these forces depends on the frequency of action and
the properties of the reaction solution [17]. MFCs may be considered as We would like to thank Dr. Swagata Ghosh, Assistant Professor of
a power supply with inherent impedance or internal resistance, and English, Symbiosis Institute of Technology, Symbiosis International
power generation in this system would be related to the impedance of University, Pune, India for editing this manuscript.
the device. Due to lower impedance a higher current density is usually
obtained in shrink MFCs [138]. In another study, van der Borden et al.
concluded that alternating current with a square wave in the frequency Authors contributions
range of 0.1–2 Hz led to isolation of Staphylococcus sp. adhered to the
steel surface [164]. Wang et al. conducted the experiment on effect of All authors read & approved the final manuscript.
alternating current on the activity of electrically activated anaerobic
biofilm. Their study, examining the anaerobic biofilm grown on the Authorship statement
electrochemical microbial reactor electrodes, revealed that the high
frequency of alternating current (5 V, 30-minute duration) only All persons who meet authorship criteria are listed as authors, and all
temporarily inhibited the biofilm activity, while lower frequency authors certify that they have participated sufficiently in the work to
(100 Hz, 0.5 or 5 V) permanently disactivated the same biofilm. The take public responsibility for the content, including participation in the
activity of the electrohydrodynamic force causes biofilm to loss its concept, design, analysis, writing, or revision of the manuscript.
intercellular electron transfer network [165]. In one study of Asadi and Furthermore, each author certifies that this material or similar material
Turkman [166] direct and indirect electrical stimulation was found to be has not been and will not be submitted to or published in any other
similar in the general bacterial reaction, however, the direct bacterial publication before its appearance in the Journal of Environmental
inhibitory effect of electrical stimulation is more important than its in­ Chemical Engineering.
direct effects [166].
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