Accepted Manuscript

Title: Bio-Fenton and Bio-electro-Fenton as sustainable

methods for degrading organic pollutants in wastewater

Authors: May Kahoush, Nemeshwaree Behary, Aurélie Cayla,

Vincent Nierstrasz

PII: S1359-5113(17)31030-9
DOI: https://doi.org/10.1016/j.procbio.2017.10.003
Reference: PRBI 11175

To appear in: Process Biochemistry

Received date: 28-6-2017

Revised date: 26-9-2017
Accepted date: 6-10-2017

Please cite this article as: Kahoush May, Behary Nemeshwaree, Cayla
Aurélie, Nierstrasz Vincent.Bio-Fenton and Bio-electro-Fenton as sustainable
methods for degrading organic pollutants in wastewater.Process Biochemistry
https://doi.org/10.1016/j.procbio.2017.10.003

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Title page

Bio-Fenton and Bio-electro-Fenton as sustainable methods for degrading organic

pollutants in wastewater

May Kahoush a,b,c,d, Nemeshwaree Behary a,b, Aurélie Cayla a,b and Vincent Nierstrasz c

a
Ecole Nationale Supérieure des Arts et Industries Textiles (ENSAIT), GEMTEX Laboratory, 2
allée Louise et Victor Champier BP 30329, 59056 Roubaix, France
b
Université de Lille, Nord de France, France
c
Textile Materials Technology, Department of Textile Technology, The Swedish School of
Textiles, Faculty of Textiles, Engineering and Business, University of Borås, SE-501 90, Borås,
Sweden
d
College of Textile and Clothing Engineering, Soochow University, Suzhou, China

Corresponding author:

May Kahoush

Department of Textile Technology

Faculty of Textiles, Engineering and Business / The Swedish School of Textiles

University of Borås

Current postal address: 501 90 Borås, Sweden | visiting address Skaraborgsvägen 3, 501 90
Borås, Sweden

Tel: +46334354072

Email: may.kahoush@ensait.fr
 Highlights for the review:
 Bio-Fenton and bio-electro-Fenton processes are used for sustainable wastewater treatment
 Factors like pH, temperature and the concentration of substrate and biocatalyst have a big impact on their
efficiency
 Various organic pollutants from industrial sources, like dyes and pesticides can be treated
 The main challenge is to improve stability and life time of these methods

Abstract
In this paper, an overview of the bio-Fenton and bio-electro-Fenton processes for sustainable wastewater treatment is

provided. These two methods have been used in recent years to treat many kinds of persistent pollutants while maintaining

the sustainability in materials and power consumption compared to conventional methods, through efficient eco-designed

systems. The different kinds of electrodes used for the bio-electro-Fenton are reviewed, along with the influencing factors

affecting the efficiency of these methods, and the different designs used to construct the reactors. Moreover, the various

organic pollutants from industrial sources, like effluents from textile and pesticides facilities, treated using these processes

are also reported. However, the main challenge facing these technologies is to improve their performance, stability and

lifetime to achieve more sustainable and cost-effective wastewater treatment on pilot and large scales. More research

should be carried out to develop a better understanding of the complex kinetics associated with these approaches.

Keywords: Bio-Electro-Fenton, Biofuel, Microbial cells, Sustainable Method, Wastewater Treatment

Introduction

Water conservation is a global issue nowadays with the increasing demand of fresh water caused by increasing population

and growing industries. Billions of tons of wastewater are produced every year worldwide from domestic use in large

cities (washing and cleaning products), industrial sites (textile, food processing plants, paper and pulp industry,

breweries), agriculture (fertilizers and pesticides) and many other sources. Agriculture is the biggest water user, with

irrigation accounting for 70% of global water withdrawals. On the other hand, small-scale industries, such as agro-

processors, textile dyeing and tanneries, can release toxic pollutants into local waters [1]. Textile dyeing and wet

processing require large amounts of fresh water withdrawal and disposal of wastewater, which makes the textile industry

one of the most polluting industries to the local rivers and surroundings especially in developing countries. According to

World Water Development Report of 2015, to process 1 kilogram of textile material, around 100-150 liters of water are

required. Hence, almost 20% of freshwater pollution comes from textile treatment and dyeing [2]. Scientists are always

trying to find new approaches to treat these wastewaters efficiently with less energy consumption and lower costs. Several

methods have been used on a large scale to treat domestic and industrial wastewaters. These include floatation,

coagulation, adsorption, membrane separation process, aerobic and anaerobic biological treatment, biochemical and

physicochemical combination processes [3]. Furthermore, many types of Advanced Oxidation Processes (AOPs) have

been used since the 1980s for wastewater treatments: hydroxyl radical-based, ozone-based, UV-based, Fenton-related and

sulfate radical-based AOPs [4]. Many reviews focus on different methods used nowadays in industry, including physical,

chemical and biological approaches for wastewater treatment [3–8]. Despite their advantages, there are still many

technical issues related to these methods that need to be improved. For instance large amounts of chemicals as well as

high energy consumption are necessary to carry out the processes, which directly affect the cost of the operation as well as

the surrounding environment. In this review, we will focus on the Bio-Fenton (BF) and Bio-Electro-Fenton (BEF) as new

sustainable methods for degrading persistent organic pollutants from different industrial sources, discuss the choice of

materials and system configurations used, along with the important parameters which should be considered when applying

these methods. Beforehand, a brief description of the Fenton, Electro-Fenton, Photo Fenton and Sono Fenton processes

used for AOPs, is provided.

Fenton and Fenton-related reactions The Fenton reaction was first discovered by H.J.H. Fenton in the year 1894.

Fenton’s reagent is a mixture of ferrous ions and hydrogen peroxide (H2O2), which forms active oxygen species capable

of oxidizing organic contaminants (illustrated in equations 1, 2).

 Fe 2+ +H2O2 → Fe 3+ +OH - + OH• (1)

Fe3+ + H2O2 → Fe2+ + OOH• + H+ (2)

Hydroxyl radicals have strong oxidizing potential (E◦ = 2.8V), and they can oxidize a wide range of organic materials

from many sources. In the past few years, Fenton reaction has been used in wastewater treatment process due to its many

advantages. Indeed, the reaction time is relatively short, and hydroxyl radicals are produced chemically without any

energy input. Moreover, the Fenton reagent is available at reasonable prices. All the previous reasons make the Fenton

reaction an interesting cost effective method in many cases. In spite of these advantages, there are still some limitations

for using this process; pH control should be held to keep the medium in the right range (pH 2-3) and the ferrous ions can

be consumed faster than their generation speed which holds back the process. In addition, more pollution levels can be

produced due to added chemicals (such as iron salts) which are difficult to extract after the reaction, and these iron ions

can contribute to the formation of complexes with certain reactive species (like ferric hydroxo complex), leading to their

deactivation. Many reviews on chemical Fenton reaction and its possible applications in wastewater treatment are

available elsewhere [9–11].

1-Electro-Fenton Electro-Fenton methods include electrochemical reactions for the in-situ generation of the reagents

used for the Fenton reaction. In this process, an electrical generator is used to facilitate the ability of the cathode to reduce

the dissolved oxygen at its surface and form hydrogen peroxide; the latter then reacts with added iron ions to produce the

hydroxyl radical of the Fenton reaction. Meanwhile, at the anode, water will be oxidized. This method has many

advantages over the chemical Fenton reaction; there is no need to store hydrogen peroxide, and less sludge is formed from

the iron species and other formed complexes. However, there is gradual corrosion of electrodes, and the biggest

disadvantage of this process is the electrical power consumption, which affects directly the cost of the wastewater

treatment. Several papers review this method in detail for treating different effluents [12–14].

2-Photo-Fenton This process combines the effect of the Fenton reaction and UV-Vis radiation from UV lamps or solar

light λ< 600 nm. The photolysis of the hydrogen peroxide by wavelength λ< 310 nm produces hydroxyl radicals along

with the photo-reduction of the ferric ions to form ferrous ions, which in turn contribute to the Fenton reaction. This

creates more hydroxyl radicals compared to the classical Fenton and hence accelerates the oxidation process, which is

considered as an advantage of this process. The photo-Fenton process and its uses is detailed elsewhere [15–18].

3-Sono-Fenton: In this process, combination of the advanced oxidation via hydroxyl radical and thermal cleavage is

achieved to treat organic pollution in wastewater. The sonication process results in extreme conditions in the medium such
as high temperature and pressure, which lead to the formation of hydroxyl radicals by breaking the chemical bond

between oxygen and hydrogen atoms (in water molecule). Thus when the iron material is added to the reaction medium,

Fenton reaction takes place. Furthermore, the previous conditions generated by sonication also affect organic pollutants

and contribute to their degradation process. A detailed review on the sono-Fenton is provided elsewhere [19].

4-Bio Fenton reaction

The BF process is also one of the processes for in-situ sustainable production of hydrogen peroxide, decreasing the danger

of its transporting and storing, reducing thus the chances of accidents. This is achieved by enzymatic activity in the

presence of bio-sourced materials and, in the presence of a source of iron ions, Fenton’s reaction can occur in the medium.

BF is promising method with many other advantages: it is a sustainable method with low power consumption along with

the ability of in-situ generation of the hydrogen peroxide reducing overall financial expenses. This process is relatively

recent trend in wastewater treatment, and has been mainly used to treat dye effluents like Malachite green [20] and Acid

blue 113 [21]. The required enzyme should be able to catalyze a reaction that will produce hydrogen peroxide as main or

by-product to supply it as Fenton’s reagent. Some of these enzymes are alcohol oxidase and glucose oxidase. The most

commonly used enzyme in BF method is glucose oxidase, which is well known to catalyze the oxidation reaction of D-

glucose to form D-glucono-1,5-lactone and as a by-product of this reaction, hydrogen peroxide is released to the reaction

medium (equation 3). Thus, in the presence of ferrous ions, the Fenton reaction takes place as shown in (equation 1).
𝐺𝑂𝑋
C6H12O6 + H2O+ O2 → C6H12O7 + H2O2 (3)

To perform BF process, as mentioned in literature, no specific configuration is required (Figure 1). For example, Elhami

et al. [20] carried out their experiments in an erlenmeyer flask, which contained the reaction mixture (heterogeneous bio-

Fenton catalyst, certain concentration of Malachite green and glucose at constant temperature and stirring).

Likewise, Karimi and his team [22] used an erlenmeyer flasks containing 50 mL of reaction mixture (the desired amounts

of Malachite green dye, glucose oxidase, glucose, and FeSO4 in distilled water) at constant shaking to perform their

experiments. Meanwhile, Eskandarian et al. [21] tested the discoloration of Acid blue 113 textile azo dye (AB 113) by BF

process performed in an aqueous medium using a flask bioreactor with constant shaking and temperature.

It is worth mentioning that many of these studies were performed with enzymes in their free state, which cause some

additional steps after the treatment to denature the enzyme in the solution. Moreover, losses of enzymes cause additional

costs of the operation. Hence, an immobilization process of enzymes is advised to achieve the reusability of these bio-

catalysts and to facilitate the extraction of the proteins from the reaction medium when desired without any further steps.
4-1-The main parameters affecting the bio-Fenton (BF) process

There are important factors and conditions that influence the bio-Fenton reactions, which are listed below and should be

taken into consideration so as to optimize the process.

4-1-1-The effect of biocatalyst concentration. In general, pollutant degradation rate increases with increasing enzymatic

load and activity in BF process, because of the direct relation between the enzyme’s activity and the in-situ production of

hydrogen peroxide that is needed for accomplishing Fenton reaction (equation 3). Elhami e al. [20] reported that the rate

constant of the reaction increased to 0.0365 min−1 by increasing the biocatalyst’s load from 1g to 2g per 100ml of the

mixture. On the other hand, excessive enzymatic activity will cause undesired reaction to occur between the active

radicals and the iron ions, which will decrease the pollutant degradation rate (equation 4). As Eskandarian et al. [21]

proved that over 3000 U/L of glucose oxidase, dye removal rate started to decrease.

OH• + Fe2+ → OH− + Fe3+ (4)

4-1-2-The effect of ferrous ions’ concentration. The concentration of Fe2+ ions affects the BF process in a similar

manner as the biocatalyst concentration. With increasing amount of Fe2+, the degradation rate increases until certain value,

above of which the rate starts to decrease due to the excessive amounts of these ions. These ions can participate in

undesired reactions and precipitate and lose their ability of performing the advanced oxidation process (equation 5). 0.4

mmol/L of Fe2+ was the value obtained by previously mentioned work [21] that above of which dye degradation rate

started to decrease.

Fe3+ + 3OH- → Fe(OH)3 (5)

4-1-3-The effect of substrate’s concentration. This parameter can be shown in the (equation 3); the hydrogen peroxide

production is proportional to the glucose concentration in the reaction medium, up to certain limits, where the maximum

rate of reaction is achieved according to Michaelis–Menten model for the enzymatic kinetics (equation 6) [23].

V max [S]
V= Km+[S] (6)

Where V is the initial rate of reaction or velocity (Mole/time), [S] is the initial molar concentration of the substrate, Vmax

is the maximum velocity attained with high substrate concentration when all the enzyme molecules are occupied and Km

is Michaelis-Menten constant (time-1).

From this equation, it can be noticed that at low substrate concentration, velocity of the reaction increases proportionally

with the concentration of the substrate. On the other hand, if the concentration of the substrate is increased further, the

velocity increases also but not proportionally until a value where the velocity is maximal and is independent of substrate
concentration. It is reported [22] that the concentration of glucose of 1.5 g/L gave the best dye discoloration when

maintaining the same conditions for Malachite green effluent. Likewise, It is found that when the glucose concentration

increased to 20 mM, the decolorization rate constant raised to Kobs = 0.0184 min-1 which is found from the slope of linear

regression of ln(C0/C) against time, where C0 and C are the initial dye concentration and the concentration at time t (min)

[20]. However, at 25 mM, the rate constant decreased to 0.0136 min-1, which is maybe due to unfavorable reactions

caused by H2O2 high concentrations.

Nevertheless, when the hydrogen peroxide is present in the reaction medium at high concentrations, certain unwanted

reactions start to occur (equation 7), which affects the global efficiency of BF reaction.

H2O2 + OH• → HO2 • + H2O (7)

4-1-4-The effect of temperature. The curve of enzymatic activity versus temperature generally is bell-shaped for most of

the enzymes. With increasing temperature, more hydrogen peroxide is produced due to increased enzymatic activity and

the rate of the Fenton reaction increases and hence, more discoloration is achieved. These observations will continue till

the optimal temperature for a given enzyme is reached, after this point the reaction slows down and eventually stops.

Some reported their experiments at constant temperature (23 ± 0.1°C) for Acid blue degradation [21], while others [20]

showed that the rate constant raised to 0.0202 min−1 when the temperature reached 40°C for the treatment of Malachite

green. It should be considered that, the optimal temperature for glucose oxidase (EC 1.1.3.4) is around 40°C, and above

this temperature, the enzymatic activity starts to decrease because of the denaturation phenomenon, which affects directly

the reaction rates. Likewise, Karimi et al. [22] found that above 30°C the decolorization rate decreased after 30 minutes

because of the denaturation of some enzymatic active sites.

4-1-5-The effect of pH. The pH value of the reaction medium is an important parameter in all enzymatic reactions.

While each enzyme functions within a specific pH range, for each enzyme there is an optimal pH value at which the

enzymatic activity is maximal (if other conditions are maintained). For the glucose oxidase (EC 1.1.3.4 ), the optimum

enzyme activity is achieved at pH 5.5. Furthermore, Fenton reaction is affected remarkably by pH values, and pH=3.5 is

considered as an optimum value according to previous studies [20].This is because H2O2 is more stable in highly acidic

conditions. Meanwhile at high pH values, precipitation of Fe(OH)3 occurs and consequently, oxidation rate decreases

because less hydroxyl radicals are available [24]. Hence, in BF reactions, a compromise between these two

considerations should be held to get the maximum efficiency from the enzymatic activity and Fenton related reactions.

It is reported that the rate constant increased from 0.0042 min−1 to 0.0194 min−1 by changing the pH value from 3.5 to
5.5 and decreased significantly above pH 5.5 for Malachite green effluent treatment using glucose oxidase [20] in

accordance of what mentioned earlier. While in another study [21], it is observed that the optimum value was pH 4 for

Acid blue effluent.

4-1-6-The effect of pollutant concentration. The pollutant concentration is also an influent factor in BF process. It was

observed that by increasing the initial pollutant concentration (the dye in the mentioned cases), the decolorization rate

increased. This can be related to the increased amount of dye molecules exposed to the Fenton reaction. Also, this causes

the hydroxyl radicals to be used in the desired reactions, and increases the rates of dye decolorization. On the other hand,

despite the increase of color removal rate, the decolorizing efficiency decreases at high concentrations of dye, due to the

constant number of hydroxyl radicals generated while the concentrations of dye molecules were increased [21].

5-Bio-electro-Fenton

In a bio-electro-Fenton (BEF) system, electrons are released due to biological activity in the anodic compartment as

shown in the (figure 2) and (equation 8) taking acetate as an example substrate [25], then these electrons are transferred

through the conductive anode to the cathode by an electrical circuit similar to conventional microbial fuel cell (MFC). In

the cathode compartment, H2O2 is continuously generated by the reduction of oxygen on the cathode, and the ferrous ions

(Fe2+) are generated in-situ by the reduction of the iron materials existing in the cathode chamber or directly on the

cathode (equations 9-10). Hence, hydroxyl radicals (HO•) are sustainably generated in-situ by the cathodic Fenton

reaction to achieve the advanced oxidation for the different effluents (figure 2).

CH3COO- + 2H2O → 2CO2+ 7H+ + 8e- (8)

O2 + 2H+ + 2e− → H2O2 (9)

Fe3+ + e− → Fe2+ (10)

From these two equations Fenton reaction can occur according to equation (1).

In addition to the previous mentioned advantages (see bio-Fenton paragraph), BEF systems have in-situ generation of the

ferrous ions needed in the Fenton reaction which can be included in the composite cathodes. This not only reduces the

amounts of excess metals and additives, but also reduces the impurities in the treated water, hence, fewer steps are needed

for filtration or precipitation of these materials. Furthermore, no power consumption is needed since the process is self-

dependent and the generation of electricity is achieved by the activity of microbial communities in the anodic

compartments.

5-1-Materials used in the bio-electro-Fenton systems

The first step for successful BEF process is the right choice of electrodes to be used as anodes and cathodes. The chosen

materials should have good stability and resistivity to corrosion in aqueous solution along with good electrical

conductivity, so as to transmit efficiently the generated electrons. Furthermore, the anode material should have

biocompatibility to achieve good adherence with the microbial societies, and should provide large surface area allowing

more contact with the growing microbes.

5-1-1-Anodes and anodic solutions

The anode materials used for BEF experiments were mainly carbon based materials, like carbon felts [26–32], carbon felts

assisted with granular graphite [33,34], polypyrrole / quinone modified carbon felts [35], graphite in the form of rods and

granules [36–38], carbon felt modified using nitric acid activation or polyaniline deposition [39], a carbon fiber brush

treated with heat as an anode for the Microbial Fuel Cell (MFC) [40], and graphite plates [41,42].

These carbon based materials used have the required conductivity and stability against solvents and electrolytes.

Furthermore, in felt form, they possess high specific surface area compared to their volume, which can help to increase

the contact area with the microbial communities used in the anodic chambers, and that enhances the electrical output of

the anodic chamber.

Microbes used on anodes

Many sources of microbes have been used to achieve the bio-activity in the constructed MFCs used for the BEF systems

in literature. Some researchers used activated Shewanella decolorationis S12 [26,35] while others used anaerobic sludge-

microbial community [32–34,36] , anaerobic seed sludge [42], Saccaromyces cerevisiae [39] and sludge from dairy

wastewater [29,31]. These microorganisms were fed constantly by mixtures of nutrients such as glucose mixed with

vitamins in acetate based buffers. In addition, other conditions such as temperature and pH used were in the favor of the

growth of these microorganisms in order to achieve constant electrical generation from their activity.

5-1-2-Cathodes

The cathode in the BEF systems has big impact on the efficiency of the cell. It is made of materials similar to those used

for anodes; with good electrical conductivity and resistant to corrosion in acidic or other mediums.

The usage of graphite rods [37], carbon felt [29,31,32], polypyrrole/ Quinone (PPy/AQDS) modified carbon felt [35],

graphite (grains and rods) with carbon paper and Platinum (Pt) [36] and carbon paper [39] have been reported. In these

cases a source of iron was added to the solution to achieve the advanced oxidation by Fenton’s reagents. However, studies

reported cathodes which are made up of composite materials bearing the iron ions within the electrode itself. When these
composite materials are exposed to the aqueous mediums, the iron starts to leach slowly, thus, ferric or ferrous ions are

released into the cathode chamber in a sustainable manner. This controlled release reduces the pollution involved when

excess iron sources are added directly into the cathodic solution, and reduces also the cost and efforts for its recuperation

from the medium when the reaction stops. Some of the recently used composite cathodes are: Fe@Fe2O3/carbon felt

composite [28,33,34,38,43], carbon felt /ɣ-FeOOH composite [27], pyrrhotite-coated graphite [30], carbon nanotubes/γ-

FeOOH composite [26] and Fe@Fe2O3/graphite composite [41,42].

Different protocols and treatments were used to produce these modified cathodes. Some articles [28,43] reported the use

of the protocol described in another work [44] for the preparation of the Fe@Fe2O3/CF (Carbon Felt) with some

modifications: the composite cathode was prepared by loading Fe@Fe2O3 on carbon felt by sonication of the CF in a

ferric solution, and then the ferric ions were reduced into metallic iron using NaBH4 solution. After that, the composite

electrode was washed in distilled water then dried in nitrogen. Almost the same protocol was used in another work [42] to

treat graphite plates. Carbon felt covered with ɣ-FeOOH as cathodes were also used [27]. This cathode was made by

mixing ɣ-FeOOH and polyvinylidene fluoride (PVDF) with 1-methyl-2-pyrrolidone solution in an ultra-sonic bath to form

a dough-like paste. This paste was then assembled into the carbon felt at high pressure and temperature of 60°C for 24 h.

Meanwhile, Li et al. [30] reported the use of silver conductive paste smeared onto the surface of polished graphite sheets.

Indeed, mineral powder (clino-pyrrhotite) was mounted on the top of the silver paste and heated under nitrogen gas, which

led to the formation of a homogeneous pyrrhotite (iron sulfide mineral) layer on the graphite surface, to be used as

composite cathode. Feng et al. [26] mixed carbon nanotube (CNT) and γ-FeOOH in several ratios with

polytetrafluoroethylene (PTFE) solution and ethanol in an ultrasonic bath to form a dough-like paste, then this paste was

assembled between two pieces of Titanium mesh at pressure of 10 MPa and 60°C to obtain the composite cathode.

5-2-Cell design used in bio-electro-Fenton systems

Studies found that the biodegradability of pollutants in wastewaters is improved by using Fenton pretreatment of the

effluents followed by biological treatment in separated processes. For example, Lucas et al. [45] used a system to combine

the effect of Fenton’s reagent followed by an aerobic biological process mediated by yeast to degrade Reactive Black

(RB5) dye, this system was capable of color removal of about 91% for an initial Reactive Black 5 dye concentration of

500 mg/L compared to 200 mg/L for the Fenton treatment alone or for the biological treatment alone. In similar way, [46]

the Fenton-coagulation process was conducted, first to reduce chemical oxygen demand (COD) of organophosphorous

pesticide wastewater and improve biodegradability, followed by biological oxidation which was achieved using moving-
bed biofilm reactor (MBBR). When wastewater with high COD values (around 33500 mg/L) was tested, removal rate was

higher than 85% while the bio-carrier volume used was more than 20%. However, the removal rate decreased to 72%

when the bio-carrier volume decreased to 10%.In spite of these studies, many researchers achieved different system

designs to operate these two treatments in one step using BEF process for wastewater treatment. Unlike the bio-Fenton,

the reactor’s design showed to be an important factor to the success of the Advanced Oxidation Process (AOP) in the BEF

process. To achieve BEF process, the main idea is to generate electrical current from the microbial activity in one part of

the system, and then use this electricity to stimulate the in-situ generation of the Fenton reagents OH. and Fe2+ to treat the

effluents. For this purpose, certain configurations are required.

A dual-chamber microbial fuel cell was used in many studies related to BEF (Figure 2) [26,27,29–31,33–35,37,39,41–43]

used a dual-chamber MFC made from different materials such as glass, Plexiglass, polycarbonate and polymethyl

methacrylate. They used different types of electrodes separated by proton exchange membrane in most of the cases. The

effective volume of each cell chamber ranged from 75ml to 600mL while working in batch mode in most of the studies.

Moreover, Zhuang et al. [28] used similar design with electrodes separated by GORE-TEX® cloth, while Zhu and Ni [32]

used 300mL glass bottles connected via glass tube with a proton-exchange membrane inside it. Xu et al. [38] designed

two coaxial cylindrical chambers separated by Gore-Tex cloth as a continuous feeding reactor (Figure 3). The anode

chamber was from the exterior and was made of plexiglass with volume of 450 ml. The Gore-Tex cloth covered the inner

chamber’s wall which had volume of 350mL. The anode chamber was continuously fed by a peristaltic pump and then the

effluent out of the anode chamber was pumped into the cathode chamber for further treatment. The effluent out of the

cathode chamber was the final effluent of the coupled system. Zhu and Logan [40] used different configuration containing

a dual reactor system with only a single-chamber MFC as low-voltage power source (Figure 4). They used a solid cube of

Lexan with cylindrical chamber for the MFC. Electro-Fenton reactors were constructed using a 100 mL bottle with no

membrane. The electro-Fenton reactor volume was about three times that of the MFC volume, unlike the classical reactors

which contain chambers of similar volume. They used a batch feeding mode to operate the Fenton reactor with the

effluents.

Another design containing two connected reactors was used by Liu et al. [36] to achieve MFC-assisted-Anodic Fenton

Treatment (AFT) system, which consists of an anodic Fenton reactor and a two-chamber air-cathode microbial fuel cell

(Figure 5). In this configuration, the power generated from two-chamber MFC was used to drive the anodic Fenton
process in the other reactor. It should be mentioned that in this study, a proton exchange membrane was used in both

reactors to separate the chambers, and the feeding mode was continuous using peristaltic pump.

5-3-The main parameters affecting the bio-electro-Fenton process

Like previously mentioned, BEF are complex systems with many linked compartments and elements, each of these

elements is affected by various conditions. Thus, all of these working conditions should be taken into consideration when

using BEF method to obtain better results in degrading organic pollutants from effluents.

5-3-1-The effect of H2O2 concentration. The in-situ generation of hydrogen peroxide is one of the most important factors

to complete the BEF process, since it can react with the ferrous ions to form the hydroxyl radicals, which in turn can

oxidize the organic pollutants found in effluents and degrade them. Studies reported that the efficiency of these systems is

mainly dependent on this factor and generally the degradation efficiency increases with the increased concentration of

H2O2. In their study [41], Birjandi et al. showed that the efficiency of Fenton’s reaction in the cathodic compartment

decreases as the molar ratio of hydrogen peroxide to total iron ions decreases, due to lack of H2O2 and consequently fewer

number of active radicals OH• are produced. Also, in another study [43] results showed that the initial addition of H2O2

also enhanced the current obtained in the system from 0.29 to 0.36 mA. On the other hand, it should be mentioned that

excessive amounts of hydrogen peroxide results in undesirable reactions to occur, and a loss of the active hydroxyl

radicals can be noticed (equation 7).

5-3-2-The effect of ferrous ions concentration. Normally, in Fenton reactions the rate of pollutants degradation is

proportional to the increase in H2O2 along with the ferrous ions concentration, due to the increased amount of OH•

formed. This can be applied until a specific value of Fe2+ concentration which can be determined experimentally, above of

which the unused iron will accumulate and contribute to an increase in the total quantity of dissolved solids in the treated

wastewaters [47]. Furthermore, these excessive ferrous ions can enter in undesired reactions which lead to the

consumption of the hydroxyl radicals as mentioned earlier (equation 4). Feng et al. [35] reported that when the

concentration of ferrous ions was changed from 1.14 to 3.43 mg/L, the rate of Orange II mineralization also increased.

Likewise, [37] the research group reported that when they increased the Fe2+ concentration from 0.1 to 1.0 mg/L, the

degradation efficiency of amaranth dye increased and confirmed the optimal concentration of the used Fe2+ is 1 mmol/L.

It should be mentioned that, to solve the issues related to the usage of iron catalysts (Fe 2+) in BEF setups like; iron-

chelating and instability of the reaction, few studies reported the use of Mn2+ as an alternative to Fe2+ according to the

equations (11,12, 13) occurring in the cathodic chamber.

 2H+ + 2e- + O2 → H2O2 (11)

Mn2+ + H2O2 + H+ → Mn3+ + OH• (12)

Mn3+ + e- → Mn2+ (13)

The results obtained showed that Mn2+ catalysts were not effective in the COD removal of the treated wastewater and no

change was detected on the COD values before and after treatment with Mn 2+, compared to 40% of COD removal after 4

hours when Fe2+ ions were used. Furthermore, the maximum power density in the case of Fe 2+ ions was 68 times higher

than that in the case of Mn2+ ions. This may be due to the ohmic polarization which minimized the effect of the Mn 2+ ions

and reduced the movement of electrons [29].

5-3-3-The effect of pH of the medium. Many researchers reported working in neutral pH in the cathodic chamber

[26,27,35,37], while others worked in a pH range of 2.7- 3 [28,30,33,38]. As mentioned previously, the optimum pH for

the Fenton reaction is around 3 since the generation of the hydroxyl radicals is most effective at acidic pH conditions [4].

The use of the neutral pH is interesting because a maximum mineralization of the organic pollutants can occur as reported

by Feng et al. [35] and also reduces the steps of the process by eliminating the pH control of the effluents.

5-3-4-The effect of temperature : most of the studies reported experiments held at 30°C for MFC [26,27,33–35], while

others reported the use of ambient temperature between 22 and 25°C [39,40]. These temperatures are mainly used to favor

microbial growth and activity. Moreover, for chemical Fenton reaction held in the cathodic compartments, studies showed

that the kinetic constants increased almost three times when temperature increased from 15 to 30°C [48]. However, more

studies should be carried to study the effect of different temperatures on the BEF systems.

5-3-5-The effect of electrode’s nature. Electrodes play a crucial role in BEF systems. Since they are in contact with the

microbial societies on one side, and with the effluents on the other side, they should provide a decent electrical

conductivity, in addition to the corrosion resistant and biocompatibility. The better the electrical conductivity, the easier

the electron transfer process occurs. Indeed, researchers found that when the electrodes were modified to get better

conductivity, the power density generated in the system improved and thus the degradation of the organic effluent was

enhanced accordingly due to a higher rate of oxygen reduction, and hence a higher rate of H2O2 production in the cathode

compartment. A study [35] indicated that there was an increase in maximum power density from 633 to 823 mW/cm2

when an intrinsic conductive polymer (PPy/AQDS) modified carbon felt was used for both the anode and cathode

electrodes instead of only the anode. Furthermore, another study [39] showed that when modified carbon felts anodes

treated with HNO3 or polyaniline were used, the power density was 2.5 to 2.9 fold higher than with unmodified
commercial carbon felt, respectively. Many studies have reported the use of composite cathodes, mainly treated with iron

materials to provide the Fenton reagent in the cathodic compartment, and to enhance the electrical behavior of the cathode

and of the system overall.

5-3-6-Power density. The power generated in the BEF systems showed to be an influencing factor on the performance of

the cell. With more power generated, the reduction of oxygen in the cathodic compartment will increase, leading to

increased generation of hydrogen peroxide, which will participate in the Fenton reaction to generate the highly active

hydroxyl radical, and thus higher degradation level of the organic materials is expected. Feng et al. [35] found that the

best rate constant of the dye mineralization kTOC= 0.256 h-1 ,which can be calculated from the natural logarithm of the

value (TOCt/TOC0) between the beginning and end of the reaction, was achieved using the system that gave the higher

power density of 823mW/cm2 with both modified anode and cathode for the treatment of Orange II dye. Further, Zhuang

et al. [28] reported that the enhancement of TOC removal of Rhodamine B was confirmed to be caused by an increase in

cathodic current density in the system, that led to increased H2O2 production. The cell that generated the higher current

density of 65.2 uA/cm2 gave better cathodic degradation rate for the RHB of kDecolorization= 0.2572 h-1 compared to 0.0675

h-1 when the current density generated was 30.1 uA/cm2 using the same type of electrodes but under different external

resistance conditions (1000 and 0 Ω respectively) . Another study [27] conducted similar observations, when higher

electrical current was generated in their system; the oxidation of Arsenite As (III) was enhanced.

5-3-8- Mass transfer limitations. In BEF systems, an interface area is needed between the microbial societies adhered on

the electrode and the nutritive medium for the bio-reactions to occur; consequently, electrons can be released from this

biological activity. This diffusion-controlled process results in complex steps of electron transfer, which in turn lead to

multiple reaction kinetics to be considered in these types of systems and some limitations related to mass transfer. In the

microbial anodic compartment, the electron transfer process can be 1) direct through electrode`s contact with the

cytochromes that are in the external membrane, 2) mediated through materials such as Flavin and Quinone, or 3) direct

through microbial nanowires [49]. Shewanella bacteria showed to be able to perform the three mechanisms, and that is

why they are commonly used in BEF systems (see paragraph 5-1-1). In batch-mode BEF systems, a decline in power

density could be attributed to the mass transfer limitations of the organic substrate to reach the microorganisms on the

surface of electrode [50]. In addition, nutrients in the medium were depleted, which led to decrease in the generated

electricity with respect to time in the anodic compartments [51]. On the other hand, mass transfer limitations can affect the

electron accepting process by dissolved oxygen in the cathodic compartments. To overcome this limitation, a study
conducted by Li et al. [30] suggested pyrrhotite-modified cathode, so pyrrhotite directly accept electrons transferred from

the anode and eliminate this problem. It worth mentioning that the cation exchange membranes between the two

compartments also can play a rule in the mass transfer, and if the proton transfer through this membrane is not fast

enough, this will cause gradual change in the pH of the anodic medium, and affect the microbial communities and power

generation [31]. To minimize the negative effects of mass transfer, it is preferred to use continuous-feeding modes for

BEF systems instead of batch-mode, to decrease as much as possible the resistance of the electrodes used to facilitate the

electron transfer process, as well as to ensure the addition of sufficient amount of mediator when used.

5-3-7-Other parameters. It should be mentioned that there are other influencing factors on the BEF process like the

external resistance applied to the system. Fu et al. [37] noticed that the degradation rates were slightly better when smaller

external resistance was used. In general, it is preferred to use a moderate external resistance to get better degradation rates

[34], and this may be because under very high or very low external resistance, the conditions in the system become

unsuitable for the bacteria and this can affect the electron acceptance process for the treated pollutant. Moreover, the

removal rate of the pollutants increases with the time of the process [28]. Similarly, with the increased the treatment time

from 15 to 120 min, degradation efficiency increased for Amaranth pollutant [37].

Environmental applications for bio-Fenton and bio-electro-Fenton

The interest in BF and BEF process has increased in the recent years. Many methods and configurations have been used to

test their efficiency in degrading organic pollutants in wastewaters from different sources and industries.

Treatment of dye solutions

It is estimated that over 10,000 different dyes and pigments are used industrially. In the textile industry, up to 200,000

tons of these dyes are lost to effluents every year during dyeing and finishing operations, due to the inefficiency of the

dyeing processes [52]. Dyes are mainly aromatic and heterocyclic compounds, with many groups to display the color.

Their structure is complex and stable, resulting in greater difficulty to degrade them. Many researchers have used the BF

or BEF process to degrade these kinds of colored pollutants to prevent their negative impact on the environment. In a

study conducted by Feng et al. [35] the decolorization and mineralization of an azo dye (i.e., Orange II) at pH 7.0 using a

dual-chamber MFC with polypyrrole (PPy)/ anthraquinone-2, 6-disulfonate (AQDS) conductive film to boost its

performance. The iron source was added to the cathode solution as ɣ-FeOOH powders and it was not included in the

cathode electrode. The stability of the cell was good for 30 days and lost about 13% of the coefficient of the Total Organic

Carbon (TOC) after 10 experiments. A study [28] reported a new BEF system in a two-chamber MFC using
Fe@Fe2O3/carbon felt composite cathode for simultaneous oxidation of wastewater at the anode, using Rhodamine B

(RhB) as a model compound and a cathodic degradation of bio refractory pollutant by Fenton’s reaction. In 12 h, RhB

color removal reached up to 95%, with about 90% of TOC removed after 12 h in the Fe@Fe 2O3/NCF cell. While

complete decolorization and mineralization of Orange II was achieved at pH 7 within 14 h [26]. For this they used a dual-

chamber MFC to power an electro-Fenton process. The electrons were generated by communities of Shewanella in the

anode chamber and transferred to its aerated cathode chamber equipped with a carbon nanotube (CNT)/γ-FeOOH

composite cathode. The fastest rate of Orange II degradation was achieved using the ratio 1:1 of CNT: γ-FeOOH,

corresponding to the highest amount of H2O2 formed. Several runs were carried to test the stability of the cell; there was a

decrease in the performance of the process during the first four runs and then it dropped dramatically in the fifth run. This

was due to gradual decline in anode performance along with the increased number of runs. As mentioned earlier, Elhami

et al. [20] prepared heterogeneous bio-Fenton catalysts from Kissiris coated with TiO2 and ferrous ions. After that,

glucose oxidase enzyme was immobilized by physical adsorption method on the modified Kissiris carrier. The

immobilized catalysts were used for decolorizing Malachite Green dye in one-compartment reactor. 99% of Malachite

Green decolorization was achieved after 120 min by using 2 g of the heterogeneous bio-Fenton catalyst and 20 mg/L of

dye, 20 mM of glucose, at pH 5.5 and 40°C. The reusability of these heterogeneous catalysts was evaluated by repeating

the process during 4 cycles in the same conditions as mentioned previously. The discoloration was up to 46% after 120

min, most probably explained by enzyme leaching and denaturation during the process. Karimi et al. also used glucose

oxidase enzyme for in-situ generation of H2O2 for the decolorization of Malachite green dye from aqueous solutions via

BF reaction in one-compartment reactor [22]. The iron source used for the Fenton reagent was FeSO4 which was added to

the reaction medium. Up to 78% of dye Decolorization was achieved within 120 min for dye concentration of 20 mg/L.

However, this decolorization process increased with increasing glucose concentration and decreased for temperatures

above 30°C due to the deactivation of some active sites of the enzyme by heat. Further, Liu et al. [36] studied the

degradation of Acid Orange 7 using a Fenton reactor with an energy supply from MFC connected to it; they found that the

increased power density resulted in increased rate of the dye degradation in the Fenton reactor. In addition, the results

showed that the Acid Orange dye did not inhibit the corrosion of the iron, since sacrificial iron was used in this study as a

source for Fenton reagent. When the kinetics of the reaction was studied, it was clear that the pseudo-first-order rate

constant fitted better to this system than the classical chemical Fenton methods. Fu et al. [37] studied the degradation of

another Azo dye which is Amaranth using MFC system. A concentrated dye solution (75 mg/L) was used and 82.59%
removal was achieved in 1 h when 1 mmol/L of ferrous ions was added to the system. When the electrochemical Fenton

was used, the degradation rate of the same Amaranth dye reached 76.4% within 1 h.

Medications and endocrine disruptors

The increased consumption of drugs in the last decade has led to increased concentration of pharmaceuticals and drugs

levels in effluent water from urban and industrial sources. These chemicals, which are also known as endocrine disruptors,

can cause serious hormonal imbalance that affects the developing fetus and may cause tumors to living organisms.

Estrogens are known as natural hormones produced in the human female body or any chemical compounds that have

similar composition or effect. These interactive materials find their way to the surface water though sewage systems,

causing big impact on environmental systems and especially aquatic species, for example fishes in high-level Estrogen

waters are being feminized [53]. In two studies, Xu et al. [33,34] worked on the removal of estrogens including 17b-

estradiol (E2) and 17a-ethynyl-estradiol (EE2) in BEF system equipped with a Fe@Fe2O3/non-catalyzed carbon felt

composite cathode. Under closed-circuit condition, 81% of E2 and 56% of EE2 were removed within 10 h in the system,

in which the highest concentration of total iron ions and H2O2 reached 81 and 1.2 mg/L, respectively. In another study, Xu

and others also achieved the removal of 17β-estradiol (E2) from water using a dual chamber BEF configuration and two

electrodes based on Fe@Fe2O3. A non-catalyzed carbon felt was used as cathode, and a carbon felt assisted with granular

graphite was used as anode which was placed in an anodic chamber filled with anaerobic sludge as biocatalyst. This

system removed over 90% of E2 after 6 h when the external resistance applied was close to the internal. In this system, it

was clear that the sorption assisted in the estradiol E2 removal in addition to the oxidation process because of the big

specific surface area of the carbon felt. While Birjandi et al. [42] designed BEF system to treat batches of medicinal herbs

wastewater which contained several kinds of pollutants such as oils and propylene glycol. When Nafion 112 membrane

was used, the maximum power density reached was 49.76 mW/m2 and the COD removal was 78% in the anaerobic anode

chamber and 84% in the aerobic process in the cathodic chamber. The higher removal of COD in the cathodic chamber is

due to the Fenton reaction occurring and producing the hydroxyl radicals with their high oxidation potential. They also

found that when the Fenton’s reagent quantities increased, the efficiency of the system in removing the COD decreased,

due to side ligands between iron and the materials in the wastewater. In another study, Zu and Ni [32] used BEF system

with scrap iron to degrade p-nitrophenol (which is an intermediate in the synthesis of paracetamol drug and also a pH

indicator) in the wastewater while generating power up to 143 mW/m2. They achieved full degradation within 12 h in this

system while the removal rate of the total organic carbon reached 85% after longer period of time (up to 96 h).
Pesticides and other pollutants

In their research, Wang et al. [27] have used a dual chamber MFC to remove Arsenite from aqueous solutions by BEF

process in neutral pH medium and controlled temperature of 30°C. Both of the Fenton reagents, H2O2 and Fe+2 were

generated in-situ. The cathode contained ɣ-FeOOH as a source of Fe2+ ions and the performance of the system showed to

be dependent on its dosage. The power density generated was 135.3 mWm2. The results showed that increasing the ɣ-

FeOOH content in the cathode decreased the generation of H2O2. The stability was good even after five cycles. In another

study [43], a dual chamber batch system was used to study the possibility of treating recalcitrant contaminants, while

generating electricity in a BEF system. The results showed clearly that Fenton’s reaction facilitated cathodic reaction and

thus increased the current output in the MFC. The power density generated reached up to 341.4 mW/m2.Also, Sw et al.

[29] used a BEF system to study the degradation of oily wastewater containing diesel oil in the cathodic chamber, while

using dairy wastewater to feed the anodic chamber. They found that with added FeSO4.7H2O as the iron source for the

Fenton reaction, 40% of COD was removed within 4 h, while the maximum power density was 102 mW/m2 in this case.

On the contrary, this process was not effective when MnSO4.H2O was used as the iron substitute for a Fenton like reaction

as mentioned earlier. In a similar configuration using both dairy and oily wastewaters, Wu et al. [31] showed that the

results are more interesting when an anion exchange membrane was used instead of the cation exchange membrane to

separate the cell compartments. They achieved COD removal of 77% within 183 h. Furthermore, the output voltage of the

system improved by at least 2 folds when compared to the results obtained using the common proton exchange membrane.

In another study [40], a BEF system powered by a single-chamber MFC to degrade phenol was used. The results obtained

showed the ability of this system to completely degrade the phenol to mainly five intermediates before continuing the

complete degradation to CO2, while some of this phenol was adsorbed or precipitated. Furthermore, almost 75% of the

TOCs were removed in one cycle (22 h) using pH 3. The power density generated from this system reached 1964 ±150

mW/m2 at pH 5 when no external resistance was used. Additionally, Li et al. [30] also used similar system to treat real ten

year-old landfill leachate with dark color, having strong odor and high COD value. 78% of COD removal was achieved

while almost 77% of dark brownish color was reduced after 45 days. The power density generated was up to 4.2 W/m3

using a pyrrhotite modified cathode. They suggested that the degradation occurred by the BEF reactions with the

involvement of other oxidants such as hydrogen peroxide but also other reactive oxygen species. Similarly, Xu et al. [38]

used BEF system to treat swine wastewater which is known for its high organic content, with COD values reaching 1652

mg/L. The power density generated with this system was 3-8 W/m3 after normalizing to the volume of the anodic solution.
They achieved good rates of removal of the COD ranging from 62.2% to 95.7% as whole system output. Indeed, the bio-

oxidation in the anodic chamber was not enough to remove all the pollutants from the swine wastewater, but further

Fenton-based treatment was achieved in the cathodic chamber to achieve the final treated effluent. Another study [41]

describe the use of glucose as synthetic COD to test its degradation in dual chamber MFC using a modified graphite

cathode. This system was able to generate power density up to 30.46 mW/m2 and removed 68.81% of the glucose in the

cathodic chamber after 12 h due to the degradation via Fenton reaction and adsorption on the used modified graphite

cathodes. Furthermore, bio-ethanol was produced from glucose in the anodic chamber with concentrations up to11.52 g/L.

Conclusion

Bio-Fenton (BF) and bio-electro-Fenton (BEF) are promising methods for the treatment of persistent organic pollutants

from many sources of wastewaters. They have been proved to be efficient in various pollutant degradation processes,

along with reduction of costs and improvement of the safety conditions of the working environment. For BF process, the

bio-materials are used to produce H2O2 in-situ, which reduces the danger of stocking and transferring. Meanwhile for the

BEF, the production of electricity FROM microbial activity is the main advantage and it provides a proper solution for the

big power consumption in electro-Fenton based systems without compromising the degradation efficiency of organic

pollutants. However, the main challenge in these systems is the low power density generated in the anodic compartments

to stimulate the Fenton reaction in the cathodic compartments. Also, the stability and the life time of these systems are

still questionable. Thus, to be able to use these methods on larger industrial scales, more research should be held to

improve the efficiency of the system, to produce more sustainable cathode materials, and to develop new methods to

produce bio-anodes to increase the power density generated by microbial societies, while the use of immobilized redox

enzymes to perform the biological activity can be useful to improve the reusability and stability needed in performance.

Acknowledgment

This work was supported by Erasmus Mundus joint Doctorate Program - Sustainable Management and Design for

Textiles (SMDTex) [grant number 2015-1594/001-001-EMJD].

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Figure legends

Figure 1. Bio-Fenton process

Figure 2. Bio-electro-Fenton system with MFC and a composite cathode

Figure 3. Schematic configuration of bio-electrochemical reactor consisting of an anodic bio-oxidation chamber and a

cathodic bio-electro-Fenton chamber adapted from Xu et al., 2011

Figure 4. Schematic diagram of the electro-Fenton system powered by a single chamber MFC adapted from Zhu & Logan,

2013

Figure 5. Working principles of the MFC-assisted-AFT system adapted from Liu et al., 2012
Figures: Figures 1 and 2 require color to be used in the printed form

Figure 1 Bio-Fenton process

Figure 2 Bio-electro-Fenton system with MFC and a composite cathode

Figure 3 Schematic configuration of bio-electrochemical reactor consisting of an anodic bio-oxidation chamber and a cathodic bio-electro-
Fenton chamber adapted from Xu et al., 2011

Figure 4 Schematic diagram of the electro-Fenton system powered by a single chamber MFC adapted from Zhu & Logan, 2013
Figure 5 Working principles of the MFC-assisted-AFT system adapted from Liu et al., 2012