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Renewable and Sustainable Energy Reviews 78 (2017) 764772

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Renewable and Sustainable Energy Reviews


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

Limits and perspectives of pulp and paper industry wastewater treatment MARK
A review
Renata Toczyowska-Mamiska
Warsaw University of Life Sciences, Faculty of Wood Technology, Department of Physics, 159 Nowoursynowska St, 02-776 Warsaw, Poland

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

Keywords: Every year the pulp and paper industry consumes billions of metres cubed of water and produces huge amounts
Microbial fuel cell of highly polluted wastewater that needs to be treated. Conventional techniques of wastewater treatment require
Pulp and paper a high energy input and their environmental impact is debatable. Thus, the need to nd new sustainable,
Pulp and paper wastewater environmentally friendly and ecient treatment techniques is urgent. Microbial fuel cells (MFC) are the
Wastewater treatment
technology of the future since they simultaneously treat wastewater and produce clean energy. The historical
Sustainable treatment
development of this technology towards its application to wastewater treatment was described. The application
of MFCs in pulp and paper wastewater treatment is a new and developing eld of investigation that still needs to
overcome many limitations before its use on an industrial scale. This article reviews the limits of conventional
treatment methods and the current state of the art MFC systems for pulp and paper wastewater treatment. The
paper provides an overview of the electrogenic microorganisms able to produce electricity from pulp and paper
wastewater. The bacteria, isolated at dierent stages of pulp and papermaking, are best suited for electrogenic
activity in harsh environments. It was shown that MFC technology fully meets the requirements of sustainable
pulp and paper wastewater treatment and, in terms of the input-output energy balance, remains energetically
and environmentally competitive when compared to conventional treatment methods.

1. Introduction and biological processes for treatment are applied. However, every
year we have to manage about 3 bln m3 of pulp and paper industry
The standards of industrial technologies and solutions determine wastewater [5](Fig. 2). The world is beginning to tighten the regula-
the condition of the environment and one's quality of life. The larger tions relating to acceptable amounts of wastewater and the toxicity of
the industry is, the more waste and pollution it usually generates, and pulp and paper mill euents. As water prices grow and environmental
the bigger the impact on the environment. Pulp and paper (P & P) standards are tightened, the global market for wastewater treatment
production has become one of the largest world industries and, in the pulp and paper sector is expected to increase from $983.9
simultaneously, it is one of the most water-related industrial sectors million in 2012 to $1.569 billion in 2020, according to an analysis by
as well as one of the most energy-consuming. The demand for paper Frost and Sullivan [6]. The conventional methods of P & P wastewater
industry products has grown over the years (Fig. 1). According to treatment deal with either secondary pollution of wastewater or high
FAOSTAT, the world production of paper in 2015 exceeded 390 mln t energy supply. Thus, P & P manufacturers have been forced to switch
[1]. Moreover, according to the prognoses, paper production is set to from the conventional wastewater treatment techniques to more
increase. The pulp and paper industry needs huge amounts of water. sophisticated ones that allow them to meet the current environmental
The water used in pulp and paper mills ranges from 5 to 100 m3 per standards. Therefore, the search for environmentally friendly and
1 t of paper produced depending on the characteristics of the ecient techniques for the P & P industry wastewater treatment is still
substrate, type of produced paper and the extent of water reuse [2]. an acute problem.
The processes of pulp and papermaking dier in dierent parts of the The objective of this article is to review the limits of conventional
world. In the modern pulp mills water consumption is typically treatment methods and the current state-of-the-art microbial fuel
between 10 and 50 m3 per 1 t of paper [3,4]. In developing countries cell (MFC) technology for P & P wastewater treatment, which pro-
larger volumes of wastewater are generated as a low ratio of water is duces clean energy. It has been shown that MFC technology can
reused and wastewater treatment is poorly organized. In the mills become key in sustainable wastewater treatment in the P & P
operating in developed countries the amount of wastewater is reduced industry.

E-mail address: renata_toczylowska@sggw.pl.

http://dx.doi.org/10.1016/j.rser.2017.05.021
Received 27 November 2016; Received in revised form 15 April 2017; Accepted 5 May 2017
1364-0321/ 2017 Elsevier Ltd. All rights reserved.
R. Toczyowska-Mamiska Renewable and Sustainable Energy Reviews 78 (2017) 764772

molecular contaminants of the synthetic polymers used in the process.


These are the unreacted monomers such as acrylamide, ethyleneimine,
unreacted chemicals used in the synthesis of the monomer units, such
as epichlorohydrin, formaldehyde and dimethylamine, as well as by-
products from the synthesis [18,19]. Acrylamide is known to be an
extremely toxic compound, and according to the International Agency
for Research on Cancer, is responsible for neurotoxic activity and
cancerogenesis [2022]. To avoid secondary wastewater pollution
caused by the addition of chemical coagulants, natural coagulants
based on polysaccharides or natural polymers (e.g. chitosan, tannins,
cellulose) were used. However, the key advantage of the bioocculants
Fig. 1. Global paper and paperboard annual production in the years 1990 2015,
i.e. biodegradability turned out to also be their great disadvantage.
according to FAOSTAT. Biopolymers have a shorter shelf life due to biodegradation through
hydrolysis, so that their treatment stability and ecacy decrease over a
relatively short time [23].
Recently, various promising membrane technologies have been
applied to P & P wastewater treatment. The most commonly used
technologies are membrane ltration, nanoltration, reverse osmosis
or membrane bioreactors [24]. The typical eciency of COD removal in
the membrane technologies ranges from 50% to 90% depending on the
membrane process used, membrane type and euent type [25].
However, the severe limitation connected with the application of the
membrane technologies is ux decline due to the membrane fouling.
Despite many eorts, this problem has not been solved and brings
about many operational consequences and high maintenance costs,
especially in the case of paper mills, where calcium concentrations in
Fig. 2. Global industrial wastewater production [7]. wastewater are relatively high. Electrochemical methods and advanced
oxidation techniques, such as ozonation and Fenton processes, allow
2. Limitations of pulp and paper wastewater conventional for COD removal over a broad range; from 60% up to 100% [26].
treatment methods However, their main disadvantage is the very high cost of treatment
caused by the huge energy input needed, reaching even 96 kW h/kg of
The conventional paper and pulp wastewater treatment includes COD removed [27].
physicochemical and biological methods [8,9]. Physicochemical treat- In order to meet the environmental demands and evade secondary
ment techniques are sedimentation, coagulation and precipitation, wastewater pollution, various biological treatment methods have been
adsorption, chemical oxidation and membrane ltration. Among the developed. They involve living microorganisms like bacteria, fungi and
physicochemical methods coagulation/occulation has been the most algae for wastewater treatment. These methods are known to be more
widely used separation technique for the removal of suspended and eco-friendly and economically attractive in comparison to the physi-
dissolved solids and organic matter from P & P wastewater [10]. In this cochemical ones. The biological methods commonly used in the P & P
process a coagulant/occulant is added to the euent which leads to industry are based on either an aerobic or anaerobic approach. Among
the aggregation and settling of the contaminants and clarication of the the aerobic methods, activated sludge processes, aerated lagoons and
wastewater. The coagulation/occulation process is connected with biological reactors are used. The activated sludge process has been the
introducing chemical coagulants, usually inorganic metal salts, such as most common biological approach for the treatment of the P & P
aluminum sulfate and ferric chloride or polyelectrolytes to the treated euents [28,29]. It deals with microorganisms cultivated in the
system [11,12]. The use of inorganic coagulants brings many dis- treatment process and is able to decompose organic matter into carbon
advantages that limit the area of their application [13]. The biggest is dioxide, water, and other inorganic compounds. Basically, the activated
the environmental impact such as the production of large volumes of sludge process requires three main elements: (1) an aerated reactor in
metalhydroxide toxic sludge that creates disposal problems and an which the suspended microorganisms are kept in contact with the
increase in metal (e.g. aluminum) concentration in the treated water, waste they treat, (2) a liquid-solid separator and (3) a sludge recycling
which may have human health implications. Additionally, as in the case system for the return of the activated sludge back to the process. The
of most physicochemical methods, the result of the treatment is high activated sludge process requires the continuous operation of oxygen
greenhouse gas emissions, that depending on the system type, can vary blowers and sludge pumps. Similarly, an aerated lagoon is a treatment
from 1.576 to 3.271 kg CO2equivalent/kg BOD for aerobic and hybrid pond where wastewater is actively aerated to promote biological
biological processes, respectively [14]. Other drawbacks of the coagula- oxidation. The greatest disadvantage of all the aerobic treatment
tion methods are a sensitivity to variations in pH, low eciency methods is the requirement of a constantly high energy supply,
towards very ne particles and low eciency in cold water [15,16]. typically 8801000 kW h per ton COD removed [30]. For example,
For these reasons polymeric occulants have been implemented. the aeration in the activated sludge process accounts for 50% of the
Commercial organic occulants are mostly linear, water soluble poly- electricity used at a treatment plant [31]. Moreover, the aerobic
mers built of repeating units of the monomers such as acrylamide and methods suer from sludge bulking and a low degree of adsorbable
acrylic acid. Commonly used polymeric occulants include polyacryla- organic halide removal (below 50%) [32]. COD removal from P & P
mide, polyacrylicacid, poly(diallyl dimethyl ammonium chloride) wastewater is typically in the range of 2070% in an aerated lagoon
(DADMAC), polyamine and others [17]. Their yield of chemical oxygen and 6097% for the activated sludge processes, depending on the type
demand (COD) removal and color removal is high - usually above 90%. of the euent used [3335].
In comparison to the conventional inorganic coagulants the use of The conventional aerobic processes have not been ecient in the
polymeric coagulants is up to ten times more expensive. However, the removal of color and recalcitrant compounds from P & P mill waste-
environmental and health costs connected with the application of the water. Other aerobic treatment methods are based on the use of fungal
polymeric occulants are even higher. The main problem is the low extracellular enzymes. COD removal from P & P wastewater with fungal

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treatment methods is typically in the range between 40% and 80% Table 1
depending on the fungus type, whereas lignin removal can be above The chemical characterization of pulp and paper manufacturing process wastewater.
90% [36,37]. However, the fungal ability for practical treatment can be
Wastewater type Chemical composition; References
restricted under extreme environmental conditions such as a high pH concentration in mg/l
and oxygen deciency [38]. Another drawback of the fungal treatment
is the high glucose requirement and longer retention time [39,40]. Mechanical and chemical COD 500115000 [6073]
pulping euents pH 6.36.8
The anaerobic digestion processes are considered to be the most
Lignin 1100025000
promising out of all the conventional biological treatment methods Sulfate 35100
[4144]. Their advantage over other biological methods, are the Sulte 504800
reduction in sludge volume by 3070%, the production of CH4 or H2 Suldes 1270
as an energy carrier, and decreased greenhouse gas emissions (250 kg Acetic acid 23510400
Resin acids 3.2550
CH4/day in anaerobic and hybrid systems), when compared to the
Chlorides 13.938.5
aerobic methods [45,46]. The COD and adsorbable organic halides Total acids 5
removal rates with the use of anaerobic digestion have achieved the Phenols 17800
levels of 7090% and 90%, respectively [47]. However, one of the main Peroxide 01000
Furfural 01140
disadvantages of anaerobic digestion technology is heat input, as it
Terpenes 0.125000
needs to operate at relatively high temperatures ( > 30 C). Moreover, 2-Propanol 018
biogas is dicult to store and needs to be treated because of the Methanol 9012000
contaminants such as H2S [48,49]. A further conversion of biogas to Ethanol 03200
electricity requires an additional step, biogas combustion (the e- Abietic acid 4.35.2
Oleic acid 5.314.5
ciency of conversion methane to electricity ranges from 30% to 40%)
-Sitosterol 2.2
[50,51]. The start up times for the anaerobic digestion processes, are Ca2+ 1727
long (months). In practice, anaerobic digestion is restricted to sludge Tannins 2730
treatment as high COD loads are required to keep reactors running at
Paper and paper recycling COD 4804450 [7481]
the optimal temperature [31]. Pre-treatment of the sludge is often
mill euents pH 6.18.3
required to increase anaerobic sludge digestibility [5254]. After time, Chlorides 80980
euents from anaerobic digestion contain high organic contents and Sulfates 241
require post-treatment [55]. Phosphates 155470
Volatile fatty acids 950
Acetic acid 200
3. Pulp and paper industry wastewater characteristics
Propionic acid 98
Butyric acid 36
The chemical composition of the wastewater from the pulp and Total polyphenols 48
paper industry diers greatly from one mill to the next. The produced Total dissolved solids 3952500
Cellulose 1200
euents are usually highly concentrated and characterized by a broad
range of COD values i.e. 0.5115 g/l [56]. The main reasons for this
are the dierent characteristics of the substrate used (e.g. hardwood or
concluded that the measured electrical current was a result of micro-
softwood species, recycled paper etc.) and the dierences in the pulping
organism activity. Although the publication was a landmark, it did not
and papermaking processes. The main steps in the paper manufactur-
get much attention as the obtained electrical parameters were low. In
ing process are: (1) pulping (mechanical, hybrid or chemical methods),
1931, B. Cohen built microbial fuel cells producing a current of 2 mA
(2) bleaching and (3) papermaking. At every stage of paper manufac-
when connected in parallel [83]. Investigations on MFC were continued
turing, euents of dierent chemical compositions are generated. Until
in the 1960s, when a system based on Clositridium butyricum fed with
now, more than 250 dierent substances have been identied in
glucose, was developed. Due to the unstable hydrogen production by
euents from pulp and paper plants [57]. A range of lignins, stilbenes,
bacteria the results were regarded as unreliable [84]. Karube et al.
phenols, dioxins, chlorides, furans, phenols and sulphur compounds
solved the problem in the 1970s by the immobilization of Clostridium
were found [58]. The euent from the pulping process, called black
butyricum in polyacrylamide gel [85,86]. However, in the late 1970s
liquor, is rich in lignin and lignin degradation products. The euents
little was known about the mechanism of current production by
from bleaching are rich in toxic compounds like adsorbable organic
microorganisms in MFC. The investigations on electron transfer within
halogens, chlorinated organic compounds, phenols etc. Delignication
MFCs were begun at the beginning of the 1980s when Bennetto et al.
processes during papermaking are the reason for the presence of lignin
revealed that power production in MFC could be greatly enhanced by
and its derivatives in the euents from paper production. Some of
the addition of electron mediators, which provided the opportunity for
these compounds are natural wood extractives like acids, tannins,
the practical application of MFC for the generation of electricity [87].
alkaloids, waxes, fats, phenols and others that are toxic compounds
As a result of a search for eective electron mediators in the late 1980s,
recalcitrant to degradation, formed during pulping and papermaking.
1990s and early 2000s, methylene blue, neutral red, thionine or other
Also, chlorinated organics e.g. dioxins or furans generated from
dyes and metallorganic compounds were investigated [8891]. Finally,
bleaching are suspected to be dangerous to living organisms as they
the mediators turned out to be toxic, expensive and unstable in MFC
can induce uncontrolled genetic mutations [59]. The substances found
systems [92]. However, a consequence of these studies were many
in the euents from pulping and papermaking, are listed in Table 1.
ndings regarding mechanisms of electron transfer and the discovery
of microorganisms such as Shewanella oneidensis, Geobacter sulfur-
4. Historical development of microbial fuel cells for
reducens or Geobacter metallireducens, that are able to transfer
wastewater treatment
electrons directly to the anode [9396]. Simultaneously, various MFC
constructions were developed and various substrates, including waste-
It has been nearly 100 years since the rst observation of the
water, were tested for power production in the MFCs [97]. It has been
electrical eects accompanying the decomposition of organic com-
found that MFCs can be successfully applied in the treatment of various
pounds by microorganisms, was made [82]. The discovery of this
types of wastewater (e.g. brewery, food processing or animal waste-
phenomenon was made by M.C. Potter on Escherichia coli and
water), and simultaneous clean electricity production [98]. As Gude
Saccharomyces cerevisiae with the use of platinum electrodes. It was

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reported, the power production in the MFC fed with wastewater was in considered to be the main elements of sustainability. Since a constant
the range from 0.2 W/m3 to 2.8 kW/m3, depending on the wastewater increase in paper production has been observed, the demand for energy
type and reactor construction [99]. The highest power densities were and water in the P & P industry should be an issue of concern. The
obtained for swine wastewater and were suspected to be strongly emission of large volumes of process wastewater charged with high
inuenced by the specic electrode circuit architecture. According to COD, and the huge amounts of energy necessary for their treatment,
Pandey et al., MFCs are able to treat particularly dangerous wastewater are main obstacles to sustainability. In addition, the low eciency and
from mining, textile, petrochemical or pharmaceutical industries [100]. high costs of conventional wastewater treatment aects the overall
In such cases, as well as electricity production, MFCs also allowed for environmental and economic ecacy of P & P production. In order to
the removal of environmentally toxic substances e.g. metals, drugs, solve the problems of water and energy usage upon wastewater
dyes or petrochemical products. However, the authors provided no treatment in the P & P industry, the principles of sustainable develop-
data on pulp and paper wastewater treatment. ment need to be implemented. One of the main paths towards a
Today MFC are commonly known as the bioelectrochemical system sustainable P & P industry is to keep the streams of process water in
producing an electric current brought about by metabolism of micro- closed-loop systems that allow for the elimination of the huge amounts
organisms [101]. The power produced in the MFCs during wastewater of wastewater produced today. However, closed-loop production
treatment is an energetic surplus [102]. From the chemical point of requires ecient, low-energy wastewater treatment techniques. A
view, MFC is an electrochemical cell where microorganisms catalyze an switch from conventional wastewater treatment to more sophisticated
electrochemical reaction (oxidation or reduction). The catalytic activity systems that allow the industry to meet current environmental
of microorganisms is exploited for electricity generation from dierent standards, is the rst step towards a sustainable P & P industry
substrates [103105]. An MFC usually consists of anode and cathode [108]. The implementation of wastewater treatment technologies into
compartments separated by a cation-specic membrane [106]. In the the industrial practice where the treatment process is accompanied by
anode compartment a substrate is oxidized by microorganisms. the generation of energy as a by-product, would be invaluable.
Electrons and protons are extra-cellularly released in the process MFCs are one of the most promising technologies in the eld of
(Fig. 3). Electrons are transferred to the electrode due to the electro- renewable energy production and wastewater treatment. Their supre-
genic activity of the microorganisms and further are transferred to the macy over other P & P wastewater treatment technologies is that MFCs
cathode compartment through an external electric circuit. The protons do not need an external energy supply, thus they have the potential to
are transferred to the cathode compartment through the proton be an energetically self-sucient and sustainable technology.
exchanging membrane. Electrons and protons are consumed in the Moreover, they allow for direct clean electricity production, with no
cathode compartment, combining with oxygen (terminal electron additional conversion needed [109]. In MFC wastewater treatment,
acceptor) to form water. Thus, MFCs harness the electrons released aeration is reduced and the treatment is possible to perform over a
by bacteria through respiration. The electricity in the MFC system is broad COD range. It has been demonstrated that MFC systems are able
generated as a result of a separation anode placed in anaerobic to remove recalcitrant organics, nutrients, sulphur compounds and
conditions (electron donor) from the cathode (electron acceptor), so metals [110116]. The start-up times for MFCs are very short as the
that electrons must pass through a resistor to reach the electron systems generate a stable power output within a few days, which is a
acceptor. The move of electrons from anode to cathode is a favorable much shorter time than for anaerobic digestion [117]. Regardless of
and spontaneous process that results in the MFC power generation. the process used for water management (an open or closed-loop
system), MFC technology meets the expectations of sustainable treat-
ment. The implementation of MFC technology into industrial practice
5. Microbial fuel cell technology towards sustainable P & P
is one of the main paths towards sustainable P & P wastewater
wastewater treatment
treatment. It allows for: (1) closed-loop production (minimization or
no fresh water usage) with recycling of the process water, (2) mini-
Sustainable development can be simply dened as to not use more
mized waste and wastewater production, (3) decreased energy usage
today than you can replace tommorrow or to consume less than what
and direct clean energy production during the treatment process, and
nature can replenish [107]. It is a holistic long-term strategy that must
(4) decreased greenhouse gas emissions. MFC technology, when
allow for the development of industries and safe growth of society, in
properly implemented, tuned and scaled up, can increase the sustain-
addition to protecting the environment from degradation. The avail-
ability of the P & P industry and contribute to its environmental
ability of raw materials, energy, emissions of waste and water are
benignancy.

6. Bacteria isolated from the pulp and paper mill wastewater

Wastewater from the P & P industry is more dicult to be treated


by MFCs due to its specic composition (Table 1). One of the main
issues, is the eciency of cellulose degradation, especially in the
presence of lignins which have an inhibitory eect on the activity of
microorganisms [118]. The products of lignin degradation are known
to have a negative eect on bacteria in MFC systems, and their
presence at high concentrations often hinders the metabolism of
bacteria. Lignin degradation products, such as catechol, vanillin,
phenolic compounds or ferulic acid, are known to decrease the viability
and eciency of fermentation bacteria [119,120]. Other microorgan-
ism activity inhibitors present in P & P wastewater are tannins, resin
acids, sulphur compounds, peroxide or chlorinated compounds [121].
However, numerous studies have shown that bacteria develop various
mechanisms allowing them to acclimatise and adapt in harmful
environments [122]. The isolation of bacteria which have adapted to
Fig. 3. Schematic presentation of current production from organic matter present in the P & P wastewater environment is a key factor for building ecient
wastewater during treatment process in MFC systems. MFCs for the treatment of such a type of wastewater.

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R. Toczyowska-Mamiska Renewable and Sustainable Energy Reviews 78 (2017) 764772

The prerequisite for microorganism applicability for P & P waste- was identied in the tertiary anode biolm [135]. Other strains e.g.
water treatment is their resistance to the inhibitors present in P & P Pelobacter propionicus and Desulfuromonas acatexigens recognized
euents. The most suitable source of bacteria strains that acclimate to as electrogens were also found [136]. The above ndings indicate that
such adverse environments are P & P manufacturing euents. Bacterial various bacteria strains able to operate in MFC systems can grow in the
communities are brought to the P & P production system mainly via wastewater from the P & P industry.
fresh water, bers or recycled pulp and paper streams. The operating
temperatures, ranging from 30 C to 50 C, and the presence of 7. Microbial fuel cells applied to the pulp and paper industry
substrates such as cellulose or starch, create an environment conducive wastewater treatment
to bacterial growth and development. Through the years, over 100
dierent bacteria strains have been isolated from the wastewater The pioneer in using MFC technologies for the treatment of the
collected at the dierent stages of pulp and paper production and pulp and paper industry wastewater was the Logan group from
wastewater treatment i.e. raw wastewater, clarier wastewater, Pennsylvania State University. The rst approach was described by
activated sludge, pulp, slimes, paper and pulping machines [123]. Huang and Logan in 2008 [79]. A single-chamber 300-ml MFC with a
Among the isolated bacteria, strains with the ability to degrade toxic graphite brush anode and air-cathode was used for the treatment of
compounds and electrogenic strains, have been found. paper recycling wastewater with simultaneous electricity production in
In the aerated stabilization basin and settling pond of the Kraft mill a batch mode. The substrate for the MFC was the paper recycling
Ancylobacter aquaticus, Klebsiella (Klebsiella terrigena and Klebsiella wastewater collected from the primary clarier that was used both as
pneumoniae), Methylobacterium spp, Pseudomonas and Comamonas the sole inoculum and as the fuel. No other microorganisms to form an
strains were isolated [61]. Most of those strains exhibit the ability to anode biolm were applied. The removal of the total COD increased
degrade lignin derivatives and chlorinated organics. The metabolic from 29% to 76% when a phosphate buer was added to the waste-
ability towards benzoate was found for Comamonas strains, the water. The obtained maximum power density was ca. 144 mW/m2 in
Klebsiella species and an unidentied bacteria cluster. Aromatic the unamended wastewater, and ca. 672 mW/m2 in a buered solution.
substrates were easily degraded by Pseudomonas strains, in addition It was reported that power and treatment eciencies were strongly
to its ability to use 2-chloroethanol as a carbon source. A. aquaticus aected by the solution conductivity. Huang et al. presented investiga-
strains also degraded 2-chloroethanol and members of the unidentied tions on reducing organic loads in the paper recycling wastewater
group utilized chloroacetate. A. aquaticus was also isolated from the accompanied by electricity production in a continuous ow MFC
inuent and euent of an aerobic P & P wastewater treatment pond system [80]. COD removal with the unamended wastewater was ca.
[124]. The strain was found to be capable of degrading methanol, 26% and the power generation was 210 mW/m2 at a hydraulic
formate and glucoisosaccharinic acid, known as a recalcitrant substrate retention time of 6 h. The continuous power production and COD
from the Kraft paper mill wastewater [125]. Both Klebsiella and removal in an MFC system is a very attractive approach from the
Bacillus species have been found in the paper mill sludge, and their technological point of view. However, the authors indicated the need
lignolytic enzyme activity was demonstrated [126]. for pilot-scale tests for the evaluation of process factors and design of
A gram-positive bacterium Brevibacillus agri, a member of the MFC construction for larger-scale systems of practical signicance.
Firmicutes, was isolated from the pulp and paper wastewater treatment Wastewater from a pulp mill was also treated in a 450-ml MFC
sludge [127]. The lignin-degrading activity of the strain was proved in a system with graphite plates as the working electrodes [134]. Bioanodes
decoloration assay for the presence of ligninolytic enzymes. The were formed under constant potential and the system operated in a fed
reduction of COD in paper wastewater by the isolated bacteria strain batch mode. In the MFCs with euent collected from the outlet of the
reached the level of ca. 62% at a retention time above 32 h. The lignin pulp mill wastewater treatment line, supplemented with a phosphate-
reduction was ca. 30% at a retention time above 30 h. The Brevibacillus buer based medium, high current densities above 5 A/m2 were
agri strain had been previously found to be dominant in the microbial obtained. Nevertheless, an investigation of COD removal was not
fuel cell using ferricyanide, which may also suggest a potential undertaken. Very interesting results were obtained by Ketep et al. in
electrogenic activity of this strain [128]. The taxa Firmicutes were also a continuous mode 500-ml MFC fed with the euent from a recycled
found to be responsible for the generation of a high power density of paper producing mill [81]. Microbial bioanodes were also formed
4.31 W/m2 in MFC using the aerated ferricyanide cathode solution and under constant potential, but without any addition of nutrients or
graphite electrodes [129]. Mehta et al. isolated the gram-negative minerals. Thus, wastewater was used as the sole inoculum and
bacteria, Alcaligenes faecalis, from the treated paper mill euent [78]. substrate source. High current densities of 4 A/m2 and COD removal
The strain was shown to have a denitrication ability. Alcaligenes up to 91% were obtained. However, low coulombic eciencies (825%)
faecalis has already been used in a dual MFC chamber with graphite were yielded. A paper mill euent treatment with simultaneous power
brush electrodes, where its electrogenic ability was evidenced [130]. generation was also studied in a single chamber bioelectrochemical
However, the mechanism of electron transfer by this bacteria is still not system with a working volume of 500 ml [75]. The MFC was based on
clear. It was hypothesized that electron transfer may be realised by the graphite electrodes and operated in a fed batch mode. Before the
transfer of electrons through the outer membrane proteins, or electrons system's performance stabilization, it operated on the synthetic waste-
may be transferred into the cell which may generate reductive water based on a supplemented phosphate buer solution, which was
compounds like NADH (reduced -nicotinamide adenine dinucleo- further substituted with a ne paper mill euent. It was observed that
tide), via biological pathways. the eciency of wastewater treatment with the use of microbial fuel cell
In the primary clarier of pulp and paper wastewater treatment was higher in comparison to the conventional anaerobic treatment
system the Enterobacter cloacae strain was found [131]. The E. process. The COD eciency removal in the MFC-based system was
cloacae strain has been successfully applied in MFC systems to produce 59% whereas the conventional treatment yielded 41%. The removal of
electricity from cellulose [132,133]. Although the cellulolytic and nitrates, phosphates and sulfates was 34%, 33% and 58%, respectively.
electrogenic activity of E. cloacae has been reported, the COD removal The yields were higher than those found for the anaerobic digestion
eciency for this strain has not yet been studied. process. Simultaneously to the treatment process, the maximum power
Such genera as Clostridium, Desulfuromonas, Pseudomonas, production in the system was 40.2 mW/m2 that corresponded to the
Geobacter, Dechloromonas, Fluvicola, Fusibacter, Aquimonas, current density of 180 mA/m2 observed at pH 7.
Flavobacter and Cryomorphaceae have been isolated from the primary The paper mill euent was also treated in a single chamber MFC of
anode biolm of MFC for the Kraft pulp mill euent treatment [134]. 45 ml volume operated in a batch mode [137]. A carbon cloth was used
Geobacter metallireducens - known as a model electrogenic strain - as an anode and the cathode was made from the modied carbon

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Table 2
Energy balances in selected industrial processes of wastewater treatment.

Wastewater treatment process type Energy consumption [kWh/kg COD] Energy production [kWh/kg COD] Wastewater type References

Aerobic treatment 0.81 0 Pulp and paper effluent [32]


[71,151]
Activated sludge processes 0.30.6 0 Domestic wastewater [152]
Modied activated sludge processes 0.21.4 0 Municipal wastewater [30]
Membrane processes 1 0 Paper mill effluent [153]
6 0 [154]
Oxidation techniques: ozonation 411 0 Pulp and paper effluent [27,155]
Electrochemical methods 6.6 0 Pulp and paper effluent [156]
2035 0 [157]
Electrocoagulation 1.19 0 [158,159]
Anaerobic digestion 0.0250.1 0.20.4 Pulp and paper effluent [160163]
MFC technologies 0.020.07 up to 0.17 Municipal wastewater [164166]

paper. The paper wastewater was used as a substrate for the MFC within several days in comparison to a few months needed for the
microorganisms while anaerobic digestor sludge from a domestic anaerobic digestion. Direct electricity generation allows for energy
wastewater treatment plant was used as the inoculum for biolm savings in comparison to the anaerobic digestion where methane is
production. The maximum current production was 125 mA/m2, and converted into electricity with the eciency of ca. 35%.
was the highest when compared to the other researched wastewaters The application of the MFC systems to P & P wastewater treatment
(brewery, bakery and dairy). The maximum power production reached is still in its infancy and there is a need to overcome numerous
60 mW/m2. The COD removal in the paper wastewater-fed MFCs was obstacles before its transfer to an industrial scale. Firstly, pulp and
78%. Biolm DGGE proles revealed dierences between the nger- papermaking euents are very dicult and complex substrates,
prints of anode bacterial communities grown on the paper wastewater- composed of numerous substances toxic to microorganisms employed
fed MFCs and those grown on other substrates. This demonstrates that in MFCs e.g. adsorbable organic halides, tannins or resin acids. It is
bacterial biolm composition strongly depends on the wastewater used important to isolate bacterial consortia able to (1) adapt to severe
as a substrate. Enhanced current production in paper wastewater-fed environmental conditions, (2) retain the ability to degrade toxic
MFCs was related to higher electroactivity of the developed micro- compounds and (3) express electrogenic activity. The best source of
organisms or to the accumulation of redox shuttles in the wastewater. such bacteria consortia are the euents generated at dierent stages of
Electrochemical analyses revealed that the environment in the MFCs the pulp and papermaking process. Additionally, detailed investiga-
fed with paper wastewater allowed for the development of anodic tions into the removal of COD, adsorbable organic halides and
communities that were electrochemically active and produced redox nutrients from P & P wastewater by MFCs, needs to be done. The
shuttles. volumetric power density obtained in an MFC for wastewater treatment
is usually in the order of several W/m3, which is much lower than the
8. Conclusions targeted kW/m3 for energetic self-suciency. Nevertheless, MFC
technology energy balance has great potential to be improved and at
The pulp and paper industry is the world's third biggest industrial present is competitive with other industrially applied wastewater
wastewater producer that generates 42% of global industrial waste- treatment methods (Table 2). MFC volumetric power densities need
water [138]. Stricter environmental demands force pulp and paper to be increased, preferably by designing more eective MFC setup
manufacturers to switch from the traditional wastewater treatment constructions, as well as novel electrode arrangements. Additionally, a
systems to more sophisticated techniques. Sustainable treatment is one strong inuence of electrolyte conductivity on current production in
which does not create secondary wastewater pollution (there is no need MFC systems has been observed in P & P wastewater treatment and
to add chemicals to wastewater during treatment) and there is no need was found to be a serious problem in the industrial scale treatments.
to supply external energy for the process. The MFC technology meets Currently, the MFCs used in P & P wastewater treatment are character-
these expectations and has the potential to lead the search for new, ized by low reactor volumes and their implementation on an industrial
environmentally friendly treatment techniques for the wastewater of scale requires detailed studies. Nevertheless, the overall characteristic
the P & P industry. Moreover, the approach brings about ecient COD of MFC technology seems very promising and as such is considered to
removal accompanied by simultaneous electricity production. MFCs be benecial [143]. MFCs can also be used as a complementary
operate in anaerobic conditions and thus do not need energy-consum- technology for other treatment techniques. According to Li et al. the
ing operations such as the aeration process which is indispensable in integration of MFCs with anaerobic digestion may allow for more
the conventional wastewater treatment via biological processes. Since ecient sludge treatment and provide more utilizable substrates for
MFCs are the anaerobic systems, bacterial biomass production is electricity generation in MFCs, e.g. volatile fatty acids [144]. High-
reduced in comparison to the aerobic treatment. Not only do MFCs load-wastewater can rstly be directed to an anaerobic digestion
not need an energy supply, but they produce clean energy during the reactor and then, after decreasing the load, can be post-treated in an
wastewater treatment process. MFC technologies have the potential to MFC system. Durruty et al. proved the eectiveness of MFCs as a
become the most promising anaerobic treatment technique as they are complementary step for methanogenesis that allowed for a signicant
more favorable to competitive anaerobic digestion. They produce decrease in the organic load of the nal euent (over a 90% decrease of
electricity directly, whereas anaerobic digestion needs a separate co- the total COD in the original wastewater) [145]. Li et al. also reported
generation plant, due to the generation of air pollutants e.g. nitrous that algal treatment in connection with MFCs, is especially ecient in
oxides. MFCs have been shown to work in termophilic, mesophilic as removing heavy metals, nitrogen and phosphorus with the eciencies
well as psychrophilic temperature ranges while aerobic digestion is reaching even 99% [144].
remarkably less ecient below 30 C and inecient at 20 C [117,139 The MFC technology can be also coupled with other treatment
142]. MFCs can operate over a wide range of COD loadings, while techniques, known for their high treatment eciency, but energy-
aerobic sludge processes are limited to sludge treatment, and their start consuming, such as membrane bioreactors (MBR) that require 0.8
up times are relatively short, as a stable power output is obtained 1.1 kW h/m3. Such an integrated system is known as bioelectrochemi-

769
R. Toczyowska-Mamiska Renewable and Sustainable Energy Reviews 78 (2017) 764772

cally-assisted membrane bioreactor [146]. Coupling an MFC with an 2000;40:4660.


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