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Microbial Fuel Cell
CHAPTER 9
Microbial Fuel Cell: A Boon in Bioremediation of Wastes Komal Agrawal1, Nisha Bhardwaj1, Bikash Kumar1, Venkatesh Chaturvedi2, Pradeep Verma1 1
Bioprocess and Bioenergy Laboratory, Department of Microbiology, Central University of Rajasthan, Kishangarh, Ajmer Rajasthan, India; 2SMW College, MG Kashi Vidyapeeth, Varanasi, Uttar Pradesh, India
Microbial Fuel Cell (MFC): A Clean Technology toward a Green Environment.
1. Introduction The increasing demand and uncontrolled use of the fossil fuel has resulted in the depletion of carbon and renewable natural resources. The concerns of Greenhouse Gas Emission (GHGE) and utilization of fossil fuel is increasing, and pressure has been imposed on the environment thereby disturbing the ecological balance. Hence the interest has diverted toward the development of clean technology favors the goal of green environment Microbial Wastewater Treatment. https://doi.org/10.1016/B978-0-12-816809-7.00009-9 Copyright © 2019 Elsevier Inc. All rights reserved.
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176 Chapter 9 (Oh et al., 2010). Microbial Fuel cell (MFC)/Biological Fuel cell (BFC) technology is one such alternative which can help to achieve the goal of clean environment along with being economically feasible. MFC through the catalytic reaction mechanisms of microorganisms (bacteria, fungus, green algae, and cyanobacteria) (Qiao et al., 2017; Wu et al., 2012; McCormick et al., 2011) helps in the conversion of the stored energy in to the chemical bond of organic or inorganic compounds to electrical energy through step by step reactions where the electrons are then transferred to a terminal electron acceptor to generate electricity (Allen and Bennetto, 1993; Gil et al., 2003; Torres et al., 2009; Chaturvedi and Verma, 2016). The microorganisms have been utilized both as a single culture and mixed consortia. The mixed cultures usually are identified via molecular techniques from the contaminated effluent used as substrates in MFC. Saccharomyces cerevisae and Escherichia coli were used for power generation by Potter (1911). It has however been observed that the mixed cultures are more productive than the pure cultures, as the condition of sterility is must incase of the later, which increases the expense (Chaturvedi and Verma, 2016). The utilization of the renewable energy resources is the only way which can help to solve the crisis of the global warming (Fig. 9.1) (Lovley, 1993; Davis and Higson, 2007; Du et al., 2007).
Figure 9.1 MFC a green approach toward minimizing various environment threats and problems.
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1.1 Fundamentals of MFC The MFC is an eco-friendly approach which helps in the generation of low voltage electricity (Agrawal et al., 2018) The MFC consists of cathodic and anodic compartment separated by a Cationic Exchange Membrane (CEM)/Proton Exchange Membrane (PEM) (Gil et al., 2003; Du et al., 2007). The microorganisms are inoculated in the anodic compartment where the metabolization of the organic compounds generates electrons and protons. The electrons mitigate by means of cathode via electrical circuit, on the other hand protons migrate through the electrolyte through the cationic membrane. The load placed between the two electrode compartments helps in harnessing the electrical energy (Allen and Bennetto, 1993). As in case of MFC, liquid wastewater or effluents are used and does not involve carbon dioxide emission, the problem of emission of green house gases is nullified (Du et al., 2007). Biofuel cell can be of two types MFC and Enzymatic Biofuel Cell (EBC). In comparison to MFC, the EBC has limited lifetime due to the sensitive nature of the enzyme. However, various techniques have been developed which can help increase the lifetime which includes immobilization and encapsulation of concerned enzyme. EBC have high power density (PD) as compared to the MFC but can only partially oxidize the fuel due to its short operational duration (Minteer et al., 2007). The MFC on the basis of construction can be of two types i.e., single and dual chambered. In a single chamber the cathode and anode are in the single chamber whereas in dual chamber they are in individual chambers. The reduction of oxygen at the cathode can be enhanced by the use of platinum or cheap metals; however, as the previous being expensive and the later being susceptible to adverse environmental conditions their applicability has limited usage. Thus an effective alternative to the noble metals can be biocathode (Chaturvedi and Verma, 2016) which can treat wastewater in the presence of terminal electron acceptors except oxygen such as recalcitrant wastes e.g., azo dyes (Sun et al., 2011a,b).
1.2 Substrates Assisted MFC A variety of substrates can be used in MFC and plays a very integral part in MFC as it has an impact on the integral composition as well as the performance including PD and Coulombic Efficiency (CE) (Chae et al., 2009). Initially low molecular weight substrates were used e.g., carbohydrates: glucose, fructose, xylose, sucrose, maltose and trehalose (Kim et al., 2000a,b; Chaudhuri and Lovley, 2003) organic acids: acetate, propionate, butyrate, lactate, succinate and malate (Holmes et al., 2004a, b; Min and Logan, 2004; Bond and Lovley, 2005), alcohol: ethanol and methanol (Kim et al., 2007) and inorganic compounds: sulfate (Rabaey et al., 2006). As the research continued complex substrates like starch, cellulose, dextran, molasses, chitin and pectin (Niessen et al., 2005, 2006;
178 Chapter 9 Table 9.1: Various substrates utilized by MFC. Sl. No. 1 2 3 4 5 6
7 8 9 10
Substrate Glucose, fructose, xylose, sucrose, maltose and trehalose Acetate, propionate, butyrate, lactate, succinate and malate Ethanol and methanol Sulfate Cellulose, dextran, molasses, chitin and pectin Starch processing wastewater, meat packing industry, swine farms and food processing and potatoproducing. Domestic wastewater Selenite and Nitrate Protein-rich wastewater Synthetic wastewater Beer brewery wastewater
References Kim et al. (2000a); Chaudhuri and Lovley (2003) Holmes et al. (2004a,b); Min and Logan (2004) Kim et al. (2007) Rabaey et al. (2006) Niessen et al. (2005); Niessen et al., 2006; Rezaei et al. (2007) Gil et al. (2003); Liu et al. (2004); Min et al. (2005); Oh and Logan (2005); Rabaey et al. (2005a,b); Heilmann and Logan (2006). Oh et al. (2010) Rovira et al. (2008); Jiang et al. (2017) Chaturvedi et al. (2014) Sun et al. (2009) Lu et al. (2017)
Rezaei et al., 2007) were used. Further wastewater from starch processing industry meat packing industry, swine farms and food processing and potato-producing units were also used (Gil et al., 2003; Liu et al., 2004; Min et al., 2005; Oh and Logan, 2005; Rabaey et al., 2005a, b; Heilmann and Logan, 2006). Liu et al. (2004) was the first to set up MFC based on domestic wastewater without actively feeding air into a cathode chamber (Oh et al., 2010). Of the various substrates used acetate is most commonly used simple substrates and is the end product of several metabolic pathways. On the other hand glucose is the primary source of carbon it is utilized very fast resulting in a short run in MFC which is usually not desirable. The focus has diverted and expanded toward a huge array of substrates (Table 9.1) however it is yet to be fully discovered and with the implementation of latest technologies many areas will be explored which would enable better power generation (Pant et al., 2010).
1.3 Mediators in MFC The nonconductive lipid membrane i.e., peptididoglycans and lipopolysaccharides on the outer layers of the microorganism inhibits the direct flow of electrons to the anode (Davis and Higson, 2007). The mediators are reduced from its oxidized state by capturing the electrons from within the membrane. The mediators then move across the membrane releasing electron to the anode, oxidizing the mediator again in the anodic chamber (Fig. 9.2), the cycle is repeated thereby increasing the power output. Thus, for enabling the
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Figure 9.2 The role of mediator in electrical conductivity in MFC.
above-mentioned process to occur certain characteristic features should be possessed by the mediators as described in Fig. 9.3 (Ieropoulos et al., 2005). Various types of synthetic mediators have been used which includes metal-organics e.g., neutral red, methylene blue, thionine, meldola’s blue, 2-hydroxy-1, 4-naphthoquinone, and Fe (III) EDTA (Park and Zeikus, 2000; Tokuji and Kenji, 2003; Ieropoulos et al., 2005). Apart from the synthetic mediators naturally occurring compounds and microbial metabolites (endogenous mediators) can also act as mediator’s e.g., humic acid, anthraquinone, oxyanions of sulfate, and thiosulphate.
Figure 9.3 The desired features of an ideal mediator.
180 Chapter 9 Microorganisms can also be used as mediator which can transfer electrons directly to the anode Chaudhuri and Lovley (2003) (Table 9.2) e.g., Shewanella putrefaciens (Kim et al., 2002), Geobacteraceae sulferreducens (Bond and Lovley, 2003), Geobacter metallireducens (Min et al., 2005), and Rhodoferax ferrireducens (Chaudhuri and Lovley, 2003). The microorganisms are bio-electrochemically active and form biofilm on the surface of anode. It then mediates the transfer of electrons directly by conductance through the membrane and act as final electron acceptor in the biofilm which occurs due to the involvement of the dissimilatory respiratory chain of the microbes. On the other hand formation of biofilms on the cathode surface also plays an important role in mitigating electrons between microbes and electrodes, e.g., Thiobacillus ferrooxidans (Prasad et al., 2006), G. metallireducens, and G. sulfurreducens (Gregory et al., 2004) seawater biofilms (Bergel et al., 2005; Du et al., 2007). Table 9.2: Various microorganisms employed in the MFC for the generation of electricity. Microorganisms
References
Pseudomonas aeruginosa Escherichia coli Shewanella sp. Nocardiopsis sp. Streptomyces enissocaesilis Geobacter metallireducens Alcaligenes faecalis Enterococcus gallinarum Leptothrix sp. Brevibacillus agri Vibrio sp. Pseudoalteromonas sp. Shewanella oneidensis Clostridium cellulolyticum Geobacter sulfurreducens Cupriavidus basilensis Pseudoalteromonas sp. Marinobacter sp. Oseobacter sp. Bacillus sp. Thiobacillus ferrooxidans Klebsiella variicola Methanocorpusculum Mycobacterium Enterobacter Stenotrophomonas Enterobacter cloacae Staphylococcus sp. Virgibacillus sp Aeromonas hydrophila
Qiao et al. (2017) Sharma et al. (2008) Chen et al. (2016) Hassan et al. (2012) Logan (2005) Kim et al. (2007) Phung et al. (2004) Aelterman et al. (2006) Logan et al. (2005) Watson and Logan (2010) Ren et al. (2007) Friman et al. (2013) Dubey et al. (2015)
Ulusoy and Dimoglo (2018) Islam et al. (2018) Wang et al. (2018)
Toczyłowska-Mami nska et al. (2015) Vijay et al. (2018) Li et al. (2017)
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2. Application of MFC for Treatment of Various Organic and Inorganic Wastes The utilization of organic and inorganic substrates in MFC has been reported by various researchers and the use of MFC involves three main advantages which include: (1) treatment of wastewater, (2) electricity generation, and (3) carbon neutral (Fig. 9.4). In the following section different organic and inorganic waste which can be efficiently utilized as substrate in MFC for electricity generation has been discussed.
2.1 Bioremediation of Chromium Released From Industrial Wastewater Using MFC Chromium is released in huge amounts from a large number of industrial effluents such as leather tanning, metallurgy, electroplating industries, and as wood preservatives (Humphries et al., 2004). It is carcinogenic and mutagenic in nature. It occurs in two forms the more toxic Cr (VI) and the less toxic Cr (III). The detoxification can be done by MFC which would involve the conversion of Cr (VI) to Cr (III). The acidic hexavalent chromium Cr (VI) has also been applied as the cathodic electron acceptor in the MFC. The study conducted by Tandukar et al. (2009) involved the reduction of Cr (VI) in the cathode, and it was inferred that the power output at Cr(VI)-contaminated sites was less in comparison to when conventional anaerobic or aerobic process were used (Molokwane et al., 2008; Tandukar et al., 2009).
Figure 9.4 Typical setup of an MFC in the treatment of wastewater and simultaneous electricity generation.
182 Chapter 9 It was observed that increased cathode surface area and small anode improved power production (Rismani-Yazidi et al., 2008). The large cathodic surface allowed the packaging of more electrochemically active microorganisms which in turn provided the bacteria and Cr (VI) with more reaction sites resulting in its reduction and power generation. In many studies, fiberous and granular graphite have also been used to enlarge the surface area of biocathode for O2 reduction and enhanced power production (You et al., 2009). Therefore, the use of graphite granule may increase power production and Cr (VI) reduction rate. A two-chamber MFC reactor by Wang et al. (2008) was set up for Cr (VI) reduction using contaminated soil as the inoculum. Chromium reduction in the presence of anaerobic sludge was studied; Cr (VI) (100 mg/L) was completely removed within 48 h of incubation with maximum PD of 767.0 mW/m2 (Xafenias et al., 2015).
2.2 Exploring the Role of MFC in the Removal of Selenite and Nitrate From Wastewater The pollutants generated and released in the environment by the industries have raised concerns globally. Among them the two pollutants selenite and nitrate can be efficiently removed by MFC: Selenite: The glass manufacturing, electrical industries, sewage sludge, fly ash from coalfired power plants, oil refineries, and mining of metal ores (Hamilton, 2004) release effluent which are rich in selenite (SeO3) and selenate (SeO4). The selenite which is disposed is more toxic in nature in comparison to selenate. Selenites easily bioaccumulates in the plants and is toxic to aquatic invertebrates and fishes (Riedel et al., 1991; Hamilton, 2004). Ground water is the major source of drinking water throughout the world, the pollution of which would affect the quantity and the quality of life causing both chronic and acute toxicity. Thus, MFC can be an effective technology for the efficient removal of selenite (Kashiwa et al., 2000; Catal et al., 2008; Rovira et al., 2008). Nitrate: The poultry and agricultural industry has led to increased discharge of nitratebased fertilizers and agro residues in the water bodies (Chebotareva and Nyokong, 1997). This when enters the food chains and the intake by the pregnant females can led to the delivery of child suffering from “blue baby syndrome” and can even be carcinogenic to the humans (Rocca et al., 2007). The use of MFC and reduction of nitrate to nitrite or nitrogen gas occurs at the cathode, researchers have employed a metal catalyst (Polatides and Kyriacou, 2005) or microorganisms as catalysts on cathode electrode (He and Angenent, 2006). In the work by Jiang et al. (2017) an autotrophic denitrifying bacterium was used for the reduction of nitrate or perchlorate with simultaneous electricity generation.
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2.3 Decomposition of Renewable Agricultural Waste by MFC and Simultaneous Electricity Generation The agricultural waste is widely available and can be of various types e.g., the waste generated from farming; poultry processing industries and agroindustries is collectively termed as agrowastes (Chaturvedi and Verma, 2016). They can be effectively used for energy production. However, the lignocellulosic biomass due to the lignin content cannot be directly used for the energy generation. The complex sugar has to be converted to simple sugar for its efficient utilization (Ren et al., 2008; Bhardwaj et al., 2017) e.g., cellulose is used for the generation of electricity via microorganisms which can produce both cellulolytic and exo-electrogenic activities (Rezaei et al., 2009). In a different study by Wang et al. (2014), the hydrosylate of rice straw was used for electricity production. The pentoses present in the agricultural residues is one of the main component of agroresidues, but an effective way for its conversion to bioethanol has not been found yet demanding more. The agrobased industries also release wastewaters that mainly consist of starch or cellulosic components. MFC may be used for the treatment of these carbohydrates polymers before its release to environment. 2.3.1 Starch industrial wastewater (SIW) treatment by MFC The starch industry wastewater consists of the following components: carbohydrates (2300e3500 mg/L) sugars (0.6%e1.2%) protein (0.1%e0.1%) and starch (1500e2600 mg/L) and can be converted to a variety of useful products (Jin et al., 1998). It can be used to generate electricity which would result in the decrease of Chemical Oxygen Demand (COD) (Kim et al., 2004). The MFC can be operated in cycles, Lu et al. (2009) obtained a maximum voltage output and PD in the third cycle out of the four cycles. On the other hand during the production of starch from cassava, high amount of starch-rich wastewater is released, having a very high COD, Biochemical Oxygen Demand (BOD), and total solid (Peters and Ngai, 2000). This starch effluent has high concentration of cyanoglycosides which hydrolyze to form cyanide. Thus, it becomes a necessity to treat the wastewater before it is released into the environment. As most of the treatment steps for the removal of cyanide are expensive the bioremediation via the MFC is an efficient and economically feasible method (Lu et al., 2009). Kaewkannetra et al. (2009) constructed an MFC and utilized cassava wastewater for the generation of electricity and efficiently removed cyanide in the process. On the other hand, it was also observed that the pH has a strong influence on the production of electricity; alkaline pH of 9 increased the power production as observed by Prasertsung et al. (2012).
184 Chapter 9 2.3.2 Cellulose industry wastewater (CIW) treatment via MFC and simultaneous electricity generation Cellulose has also been for generation of electricity via MFC (Niessen et al., 2005). Rismani-Yazidi et al. (2008) employed cellulose for bioelectricity generation using microorganisms from the rumen of cattle. Ren et al. (2008) constructed a dualchambered MFC for electricity generation using cellulose-degrading bacteria Clostridium cellulolyticum and electrochemically active bacteria Geobacter sulfurreducens. Cellulose was also utilized as substrate for electricity generation using a dual-chambered MFC by Sedky et al. (2012). Use of vegetable waste for bioelectricity production was also investigated by Clauwaert et al. (2008). Cellulose from wheat straw; rice mill wastewater, corn stover, and Canna indica can be used to some extent by electrophilc bacteria for electricity generation (Zang et al., 2010). In the study by Toczyłowska-Mami nska et al. (2018) a single-chamber air-cathode MFCs fed cellulose, was used to determine the changes in the bacterial consortium in an MFC fed cellulose over time. It was observed that the Firmicutes sp. was the most predominant bacteria for electron generation. After an extended operation the main genera developed were cellulolytic strains, fermenters and electrogens i.e., Parabacteroides, Proteiniphilum, Catonella and Clostridium.
2.4 Electricity Generation via MFC Using Slaughter House Waste (SHW) Numerous publications have reported the use slaughter house wastewater for generation of electricity (Katuri et al., 2012). SHW contains high amount of proteins, fats and carbohydrates, which is an ideal source for generation of electricity. A dual-chambered MFC consisted of SHW with an inoculum being the anaerobic mixed sludge was constructed. It was observed at a concentration of 900 mg-COD/L maximum PD of 578 mW/m2 was obtained (Katuri et al., 2012). Chaturvedi et al. (2014), studied degradation of chicken feathers by a strain P. aeruginosa with concomitant electricity production in MFC, the maximum voltage of 141 mV was observed after 14 days and the maximum PD and current density of was observed to be 1206.8 mW/m2 and 8.6 mA/m2 respectively.
2.5 Bioremediation of Synthetic Wastewater via MFC and Concurrent Electricity Generation The azo dyes are widely used in textile industries and are one of the major pollutants in wastewaters (Verma and Madamwar, 2005) and can be used as electron acceptors at cathode (Xu et al., 2007). They have the presence of - (eN]Ne) - bond, where the double bond is reduced to hydrazo (A) or amine (B), via the consumption of two or four electrons respectively. The MFC system can be more effective if the dye containing system can
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simultaneously be used for biodegrading organic matter containing wastewater and electricity generation. However, this has only been feasible at laboratory scale and requires further improvisation for its implementation at larger scale. The enzyme laccase was also used at the cathode for the efficient removal of the dye Reactive Blue 221 and simultaneous removal of molasses at the anode (Bakhshian et al., 2011). Liu et al. (2009a,b) reported the production of electricity by employing MFCs using azo dyes as the cathode oxidants and using Klebsiella pneumonia strain L17 in the anode in a dualchamber MFC supplemented with glucose. The results demonstrated that the azo dyes were successfully degraded at the cathode and the power output was dependent on the catholyte pH and the dye molecular structure. Sun et al. (2009) used active Brilliant Red X-3B for dye decolorization, however higher concentration of dye effected the electricity generation from glucose. This was due to the competition between azo dye and the anode for electrons from carbon sources. In an air-cathode single-chambered MFC, equivalent volumes of aerobic and anaerobic sludge were used as inoculum. The MFC was continuously operated at a fixed external resistor of 500 U and voltage for more than 4 months and it was observed that the cathodic potential gradually decreased over time and of the anodic potential remained same. The anaerobic cleavage of azo bond of the Congo red converted it to form aromatic amines in the presence of glucose (Chen et al., 2010; Sun et al., 2011a,b). The bacteria were identified as the members of the genera Azospirillum, Methylobacterium, Rhodobacter, Desulfovibrio, Trichococcus, and Bacteroides in the presence of Congo Red. Venkata Mohan et al. (2008) used synthetic waste in which the redox mediators such as cysteine and sulfur species were present and helped increase the power production by acting as an abiotic electron donor (Aldrovandi et al., 2009) for a short duration of time thus not representing the true performance of the MFC. Recently a new device called Coupled Constructed Wetland MFC (CW-MFC) was constructed to remove recalcitrant dye Reactive Brilliant Red X-3B wastewater and produce energy. It was observed that maximum decolorization rate and the electricity production was 95.6% and 0.852 W/m3, respectively, when the COD was 300 mg/L while the proportion of Reactive Brilliant Red X-3B was 30% (Fang et al., 2015). 2.5.1 Enzyme-mediated MFC: a new approach toward bioremediation The concept of biocathode has gained importance where the use of bacterial or fungal culture can help in the bioremediation and concurrent electricity generation. For the past few years the concept has gained much interest among the researchers and has even led to the use of laccase a p-diphenol: dioxygen oxidoreductase belonging to the family of multicopper proteins for the treatment of synthetic wastewater. As per the study by Wu et al. (2012) Coriolus versicolor was inoculated in the cathodic chamber of MFC and 2,20 Azino-bis(3-ethylbenzothazoline-6-sulfonate) (ABTS) was added as a redox mediator to the catholyte to enable electron transfer between the electrode and laccase. This study showed that the fungal-based biocathode is better than the conventional abiotic cathode,
186 Chapter 9 with as it exhibited approximately seven-order higher PD. In another study Ganoderma laccase with carbon-fiber-brush air-cathode was used to treat molasses wastewater. It was experimentally validated the laccase activity was higher 108 U/L in the presence of 125 mM of CuSO4 on day eight. The addition of crude laccase broth (420 mV) enhanced the MFC performance in terms of electricity generation more in comparison to the filtered broth (300 mV) and the set effectively maintained power generation for 45 days (Lin et al., 2018). Similarly, in the other study by Bakhshian et al. (2011), enzymatic decolorization of dye Reactive Blue 221 was done in dual chamber MFC in the absence of mediator. As the use of mediator would involve an increase in the cost associated with the MFC, mediator less MFC is more preferred over a mediator based MFC. Thus, the biocathode can be effectively used for the removal of the synthetically generated wastewater and bioremediation.
2.6 The Role of MFC in the Treatment of Brewery Wastewater The use of brewery waste has been more preferred as it does not contain ammonia which is present as incase of animal waste, low strength, food derived organic nature and lack of inhibitory substances. Brewery wastewater COD is also 10 times more concentrated than the domestic waste, has high carbohydrate content, and makes it an ideal substrate for MFC (Vijayaraghavan et al., 2006). Feng et al. (2008) used the wastewater with the help of an air cathode and a maximum PD of 528 mW/m2 was achieved with 50 mM phosphate buffer and the wastewater. In this study a comparison between brewery and domestic waste showed that the brewery waste produced less power. This may be attributed due to the difference in conductivities of the wastewater. The study conducted by Lu et al. (2017) determined long term performance by using 20L MFC consisting of brewery waste, results for 325 days indicated that the MFCs can sustain treatment rates for a long-term period and are strong enough to sustain performance even after system disturbances.
2.7 Bioremediation of Landfill Leachates and Municipal Wastewater via MFC The landfill leachates pollutants have adverse effect on the environment. It is a combination of four major pollutants which includes dissolved organic matter, inorganic macro-components, heavy metals, and xenobiotic organic compounds (Kjeldsen et al., 2002). Zhang et al. (2008) constructed an up-flow air-cathode MFC which was operated continuously for 50hr and produced volumetric power of 12.8 W/m3 and CD of 41 A/m3. Later Greenman et al., 2009 constructed an MFC column and showed electricity and simultaneous treatment of landfill leachate, whereas as Ga´lvez et al. (2009) used three chambered MFCs which were fluidically connected in series for instantaneous leachate treatment and electricity generation.
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Similarly, municipal wastewater has also generated much concern, in the study by Liang et al. (2018) the MFC was operated for a year and the volume used was 1000 L, the largest reported volume so far. In this the removal rate of COD was 70%e80% which actually met the pollution of standards for Municipal Wastewater Treatment Plants (MWTP) of China.
3. Limitations, Future Prospects, and Conclusion MFC was initially started with the purpose of utilizing microbes for power generation, but in the short span of time it evolved as a technology and is improving day by day. MFC has evolved as a “boon” not only in the area of energy generation but in the bioremediation of waste as well. The MFC for its efficient utilization in the future, the limitation which exist should be overcome. The reactor design should be modified so that efficient electricity generation at large scale with minimum cost can be implemented beyond laboratory. The low PD needs to be rectified by either isolating new potential microorganisms or through the application of DNA technology. The mediator to be used in MFC should be cheap and widely available. The cathode and the anode surface area have a very important role to play in MFC, hence more research is required which can help in the optimization of the ratio of the surface area of cathode to anode. The biocathode which involves the use of microorganisms and enzyme has to be applied at larger scale as the laccase enzyme used in EBC has a huge potential for bioremediation. A new concept of “living solar cell” proposed by Rosenbaum et al. (2005) where green alga Chlamydomonas reinhardtii produced hydrogen photosynthetically and is oxidized in situ to produce current. The “living solar cell” is an approach to convert solar energy into electric energy through photosynthetic microorganisms (He et al., 2009) or living plants along with bacteria in MFC (Strik et al., 2008). As the initiative is new it requires further study for its effective implementation in the future and commercialization. In last 2 decades MFC is used as an alternative to the conventional wastewater/waste treatment plants where they would help in bioremediation of waste along with electricity generation. Hence, making MFC a selfsustainable and energy efficient alternative to the costly energy consuming processes. However, more work is required in the areas of MFC development and with the advent of new technologies and adaptations; the evolution of MFC from laboratory to commercial scale can occur and thus be “Boon to the Real World”.
Abbreviations BFC BOD CE CEM CIW
Bio-fuel cell Biochemical oxygen demand Coulombic Efficiency Cation exchange membrane Cellulose industry waste
188 Chapter 9 COD CW-MFC EBC ETC GHGE MFC MWTP PD PEM SHW SIW
Chemical oxygen demand Coupled constructed wetland-MFC Enzymatic biofuel cell Electron transport chain Green house gas emission Microbial fuel cell Municipal wastewater treatment plants Power density Proton Exchange Membrane Slaughter House Waste Starch industrial wastewater
Acknowledgements PV is thankful to DBT (Grant No. BT/304/NE/TBP/2012; Grant No. BT/PR7333/PBD/26/373/2012) and KA is thankful to Central University of Rajasthan, Ajmer, India, for providing the financial support.
Competing Interests All the authors declare that they have no competing interests.
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Liu, H., Logan, B.E., 2004. Electricity generation using an air-cathode single chamber microbial fuel cell in the presence and absence of a proton exchange membrane. Environmental Science and Technology 38, 4040e4046. Liu, L., Li, F., Feng, C., Li, X., 2009a. Microbial fuel cell with an azo-dye-feeding cathode. Applied Microbiology and Biotechnology 85, 175e183. Liu, Z., Liu, J., Zhang, S., Su, Z., 2009b. Study of operational performance and electrical response on mediator-less microbial fuel cells fed with carbon and protein-rich substrates. Biochemical Engineering Journal 45, 185e191. Logan, B.E., 2005. Simultaneous wastewater treatment and biological electricity generation. Water Science and Technology 52 (1e2), 31e37. Logan, B.E., Murano, C., Scott, K., Gray, N.D., Head, I.M., 2005. Electricity generation from cysteine in a microbial fuel cell. Water Research 39 (5), 942e952. Lovley, D.R., 1993. Dissimilatory metal reduction. Annual Review of Microbiology 47, 263e290. Lu, M., Chen, S., Babanova, S., Phadke, S., Salvacion, M., Mirhosseini, A., Chan, S., Carpenter, K., Cortese, R., Bretschger, O., 2017. Long-term performance of a 20-L continuous flow microbial fuel cell for treatment of brewery wastewater. Journal of Power Sources 356, 274e287. Lu, N., Zhou, S.G., Zhuang, L., Zhang, J.T., Ni, J.R., 2009. Electricity generation from starch processing wastewater using microbial fuel cell technology. Biochemical Engineering Journal 43, 246e251. McCormick, A.J., Bombelli, P., Scott, A.M., Philips, A.J., Smith, A.G., Fisher, A.C., Howe, C.J., 2011. Photosynthetic biofilms in pure culture harness solar energy in a mediatorless bio-photovoltaic cell (BPV) system. Energy & Environmental Science 4 (11), 4699e4709. Min, B., Cheng, S., Logan, B.E., 2005. Electricity generation using membrane and salt bridge microbial fuel cells. Water Research 39, 1675e1686. Min, B., Logan, B.E., 2004. Continuous electricity generation from domestic wastewater and organic substrates in a flat plate microbial fuel cell. Environmental Science and Technology 38 (21), 5809e5814. Minteer, S.D., Liaw, B.Y., Cooney, M.J., 2007. Enzyme-based biofuel cells. Current Opinion in Biotechnology 18 (3), 228e234. Molokwane, P.E., Meli, K.C., Nkhalambayausi-Chirw, E.M., 2008. Chromium (VI) reduction in activated sludge bacteria exposed to high chromium loading: brits culture (South Africa). Water Research 42, 4538e4548. Niessen, J., Harnisch, F., Rosenabaum, M., Schro¨der, U., Scholz, F., 2006. Heat treated soil as convenient and versatile source of bacterial communities for microbial electricity generation. Electrochemistry Communications 8, 869e873. Niessen, J., Schro¨der, U., Harnisch, F., Scholz, F., 2005. Gaining electricity from in situ oxidation of hydrogen produced by fermentative cellulose degradation. Letters in Applied Microbiology 41, 286e290. Oh, S., Logan, B., 2005. Hydrogen and electricity production from a food processing wastewater using fermentation and microbial fuel cell technologies. Water Research 39, 4673e4682. Oh, S.T., Kim, J.R., Premier, G.C., Lee, T.H., Kim C Sloan, W.T., 2010. Sustainable wastewater treatment: how might microbial fuel cells contribute. Biotechnology Advances 28 (6), 871e881. Pant, D., Van Bogaert, G., Diels, L., Vanbroekhoven, K., 2010. A review of the substrates used in microbial fuel cells (MFCs) for sustainable energy production. Bioresource Technology 101 (6), 1533e1543. Park, D.H., Zeikus, J.G., 2000. Electricity generation in microbial fuel cells using neutral red as an electronophore. Applied and Environmental Microbiology 66, 1292e1297. Peters, D., Ngai, D.D., 2000. An DT Agro-Processing Wastewater Assessment in Periurban Hanoi, pp. 451e457. CIP program report. Phung, N.T., Lee, J., Kang, K.H., Chang, I.S., Gadd, G.M., Kim, B.H., 2004. Analysis of microbial diversity in oligotrophic microbial fuel cells using 16S rDNA sequences. FEMS Microbiology Letters 233 (1), 77e82. Polatides, C., Kyriacou, G., 2005. Electrochemical reduction of nitrate ion on various cathode reaction kinetics on bronze cathode. Journal of Applied Electrochemistry 35, 421e427.
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Microbial Fuel Cell: A Boon in Bioremediation of Wastes Komal Agrawal1, Nisha Bhardwaj1, Bikash Kumar1, Venkatesh Chaturvedi2, Pradeep Verma1 1
Bioprocess and Bioenergy Laboratory, Department of Microbiology, Central University of Rajasthan, Kishangarh, Ajmer Rajasthan, India; 2SMW College, MG Kashi Vidyapeeth, Varanasi, Uttar Pradesh, India
Microbial Fuel Cell (MFC): A Clean Technology toward a Green Environment.
1. Introduction The increasing demand and uncontrolled use of the fossil fuel has resulted in the depletion of carbon and renewable natural resources. The concerns of Greenhouse Gas Emission (GHGE) and utilization of fossil fuel is increasing, and pressure has been imposed on the environment thereby disturbing the ecological balance. Hence the interest has diverted toward the development of clean technology favors the goal of green environment Microbial Wastewater Treatment. https://doi.org/10.1016/B978-0-12-816809-7.00009-9 Copyright © 2019 Elsevier Inc. All rights reserved.
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176 Chapter 9 (Oh et al., 2010). Microbial Fuel cell (MFC)/Biological Fuel cell (BFC) technology is one such alternative which can help to achieve the goal of clean environment along with being economically feasible. MFC through the catalytic reaction mechanisms of microorganisms (bacteria, fungus, green algae, and cyanobacteria) (Qiao et al., 2017; Wu et al., 2012; McCormick et al., 2011) helps in the conversion of the stored energy in to the chemical bond of organic or inorganic compounds to electrical energy through step by step reactions where the electrons are then transferred to a terminal electron acceptor to generate electricity (Allen and Bennetto, 1993; Gil et al., 2003; Torres et al., 2009; Chaturvedi and Verma, 2016). The microorganisms have been utilized both as a single culture and mixed consortia. The mixed cultures usually are identified via molecular techniques from the contaminated effluent used as substrates in MFC. Saccharomyces cerevisae and Escherichia coli were used for power generation by Potter (1911). It has however been observed that the mixed cultures are more productive than the pure cultures, as the condition of sterility is must incase of the later, which increases the expense (Chaturvedi and Verma, 2016). The utilization of the renewable energy resources is the only way which can help to solve the crisis of the global warming (Fig. 9.1) (Lovley, 1993; Davis and Higson, 2007; Du et al., 2007).
Figure 9.1 MFC a green approach toward minimizing various environment threats and problems.
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1.1 Fundamentals of MFC The MFC is an eco-friendly approach which helps in the generation of low voltage electricity (Agrawal et al., 2018) The MFC consists of cathodic and anodic compartment separated by a Cationic Exchange Membrane (CEM)/Proton Exchange Membrane (PEM) (Gil et al., 2003; Du et al., 2007). The microorganisms are inoculated in the anodic compartment where the metabolization of the organic compounds generates electrons and protons. The electrons mitigate by means of cathode via electrical circuit, on the other hand protons migrate through the electrolyte through the cationic membrane. The load placed between the two electrode compartments helps in harnessing the electrical energy (Allen and Bennetto, 1993). As in case of MFC, liquid wastewater or effluents are used and does not involve carbon dioxide emission, the problem of emission of green house gases is nullified (Du et al., 2007). Biofuel cell can be of two types MFC and Enzymatic Biofuel Cell (EBC). In comparison to MFC, the EBC has limited lifetime due to the sensitive nature of the enzyme. However, various techniques have been developed which can help increase the lifetime which includes immobilization and encapsulation of concerned enzyme. EBC have high power density (PD) as compared to the MFC but can only partially oxidize the fuel due to its short operational duration (Minteer et al., 2007). The MFC on the basis of construction can be of two types i.e., single and dual chambered. In a single chamber the cathode and anode are in the single chamber whereas in dual chamber they are in individual chambers. The reduction of oxygen at the cathode can be enhanced by the use of platinum or cheap metals; however, as the previous being expensive and the later being susceptible to adverse environmental conditions their applicability has limited usage. Thus an effective alternative to the noble metals can be biocathode (Chaturvedi and Verma, 2016) which can treat wastewater in the presence of terminal electron acceptors except oxygen such as recalcitrant wastes e.g., azo dyes (Sun et al., 2011a,b).
1.2 Substrates Assisted MFC A variety of substrates can be used in MFC and plays a very integral part in MFC as it has an impact on the integral composition as well as the performance including PD and Coulombic Efficiency (CE) (Chae et al., 2009). Initially low molecular weight substrates were used e.g., carbohydrates: glucose, fructose, xylose, sucrose, maltose and trehalose (Kim et al., 2000a,b; Chaudhuri and Lovley, 2003) organic acids: acetate, propionate, butyrate, lactate, succinate and malate (Holmes et al., 2004a, b; Min and Logan, 2004; Bond and Lovley, 2005), alcohol: ethanol and methanol (Kim et al., 2007) and inorganic compounds: sulfate (Rabaey et al., 2006). As the research continued complex substrates like starch, cellulose, dextran, molasses, chitin and pectin (Niessen et al., 2005, 2006;
178 Chapter 9 Table 9.1: Various substrates utilized by MFC. Sl. No. 1 2 3 4 5 6
7 8 9 10
Substrate Glucose, fructose, xylose, sucrose, maltose and trehalose Acetate, propionate, butyrate, lactate, succinate and malate Ethanol and methanol Sulfate Cellulose, dextran, molasses, chitin and pectin Starch processing wastewater, meat packing industry, swine farms and food processing and potatoproducing. Domestic wastewater Selenite and Nitrate Protein-rich wastewater Synthetic wastewater Beer brewery wastewater
References Kim et al. (2000a); Chaudhuri and Lovley (2003) Holmes et al. (2004a,b); Min and Logan (2004) Kim et al. (2007) Rabaey et al. (2006) Niessen et al. (2005); Niessen et al., 2006; Rezaei et al. (2007) Gil et al. (2003); Liu et al. (2004); Min et al. (2005); Oh and Logan (2005); Rabaey et al. (2005a,b); Heilmann and Logan (2006). Oh et al. (2010) Rovira et al. (2008); Jiang et al. (2017) Chaturvedi et al. (2014) Sun et al. (2009) Lu et al. (2017)
Rezaei et al., 2007) were used. Further wastewater from starch processing industry meat packing industry, swine farms and food processing and potato-producing units were also used (Gil et al., 2003; Liu et al., 2004; Min et al., 2005; Oh and Logan, 2005; Rabaey et al., 2005a, b; Heilmann and Logan, 2006). Liu et al. (2004) was the first to set up MFC based on domestic wastewater without actively feeding air into a cathode chamber (Oh et al., 2010). Of the various substrates used acetate is most commonly used simple substrates and is the end product of several metabolic pathways. On the other hand glucose is the primary source of carbon it is utilized very fast resulting in a short run in MFC which is usually not desirable. The focus has diverted and expanded toward a huge array of substrates (Table 9.1) however it is yet to be fully discovered and with the implementation of latest technologies many areas will be explored which would enable better power generation (Pant et al., 2010).
1.3 Mediators in MFC The nonconductive lipid membrane i.e., peptididoglycans and lipopolysaccharides on the outer layers of the microorganism inhibits the direct flow of electrons to the anode (Davis and Higson, 2007). The mediators are reduced from its oxidized state by capturing the electrons from within the membrane. The mediators then move across the membrane releasing electron to the anode, oxidizing the mediator again in the anodic chamber (Fig. 9.2), the cycle is repeated thereby increasing the power output. Thus, for enabling the
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Figure 9.2 The role of mediator in electrical conductivity in MFC.
above-mentioned process to occur certain characteristic features should be possessed by the mediators as described in Fig. 9.3 (Ieropoulos et al., 2005). Various types of synthetic mediators have been used which includes metal-organics e.g., neutral red, methylene blue, thionine, meldola’s blue, 2-hydroxy-1, 4-naphthoquinone, and Fe (III) EDTA (Park and Zeikus, 2000; Tokuji and Kenji, 2003; Ieropoulos et al., 2005). Apart from the synthetic mediators naturally occurring compounds and microbial metabolites (endogenous mediators) can also act as mediator’s e.g., humic acid, anthraquinone, oxyanions of sulfate, and thiosulphate.
Figure 9.3 The desired features of an ideal mediator.
180 Chapter 9 Microorganisms can also be used as mediator which can transfer electrons directly to the anode Chaudhuri and Lovley (2003) (Table 9.2) e.g., Shewanella putrefaciens (Kim et al., 2002), Geobacteraceae sulferreducens (Bond and Lovley, 2003), Geobacter metallireducens (Min et al., 2005), and Rhodoferax ferrireducens (Chaudhuri and Lovley, 2003). The microorganisms are bio-electrochemically active and form biofilm on the surface of anode. It then mediates the transfer of electrons directly by conductance through the membrane and act as final electron acceptor in the biofilm which occurs due to the involvement of the dissimilatory respiratory chain of the microbes. On the other hand formation of biofilms on the cathode surface also plays an important role in mitigating electrons between microbes and electrodes, e.g., Thiobacillus ferrooxidans (Prasad et al., 2006), G. metallireducens, and G. sulfurreducens (Gregory et al., 2004) seawater biofilms (Bergel et al., 2005; Du et al., 2007). Table 9.2: Various microorganisms employed in the MFC for the generation of electricity. Microorganisms
References
Pseudomonas aeruginosa Escherichia coli Shewanella sp. Nocardiopsis sp. Streptomyces enissocaesilis Geobacter metallireducens Alcaligenes faecalis Enterococcus gallinarum Leptothrix sp. Brevibacillus agri Vibrio sp. Pseudoalteromonas sp. Shewanella oneidensis Clostridium cellulolyticum Geobacter sulfurreducens Cupriavidus basilensis Pseudoalteromonas sp. Marinobacter sp. Oseobacter sp. Bacillus sp. Thiobacillus ferrooxidans Klebsiella variicola Methanocorpusculum Mycobacterium Enterobacter Stenotrophomonas Enterobacter cloacae Staphylococcus sp. Virgibacillus sp Aeromonas hydrophila
Qiao et al. (2017) Sharma et al. (2008) Chen et al. (2016) Hassan et al. (2012) Logan (2005) Kim et al. (2007) Phung et al. (2004) Aelterman et al. (2006) Logan et al. (2005) Watson and Logan (2010) Ren et al. (2007) Friman et al. (2013) Dubey et al. (2015)
Ulusoy and Dimoglo (2018) Islam et al. (2018) Wang et al. (2018)
Toczyłowska-Mami nska et al. (2015) Vijay et al. (2018) Li et al. (2017)
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2. Application of MFC for Treatment of Various Organic and Inorganic Wastes The utilization of organic and inorganic substrates in MFC has been reported by various researchers and the use of MFC involves three main advantages which include: (1) treatment of wastewater, (2) electricity generation, and (3) carbon neutral (Fig. 9.4). In the following section different organic and inorganic waste which can be efficiently utilized as substrate in MFC for electricity generation has been discussed.
2.1 Bioremediation of Chromium Released From Industrial Wastewater Using MFC Chromium is released in huge amounts from a large number of industrial effluents such as leather tanning, metallurgy, electroplating industries, and as wood preservatives (Humphries et al., 2004). It is carcinogenic and mutagenic in nature. It occurs in two forms the more toxic Cr (VI) and the less toxic Cr (III). The detoxification can be done by MFC which would involve the conversion of Cr (VI) to Cr (III). The acidic hexavalent chromium Cr (VI) has also been applied as the cathodic electron acceptor in the MFC. The study conducted by Tandukar et al. (2009) involved the reduction of Cr (VI) in the cathode, and it was inferred that the power output at Cr(VI)-contaminated sites was less in comparison to when conventional anaerobic or aerobic process were used (Molokwane et al., 2008; Tandukar et al., 2009).
Figure 9.4 Typical setup of an MFC in the treatment of wastewater and simultaneous electricity generation.
182 Chapter 9 It was observed that increased cathode surface area and small anode improved power production (Rismani-Yazidi et al., 2008). The large cathodic surface allowed the packaging of more electrochemically active microorganisms which in turn provided the bacteria and Cr (VI) with more reaction sites resulting in its reduction and power generation. In many studies, fiberous and granular graphite have also been used to enlarge the surface area of biocathode for O2 reduction and enhanced power production (You et al., 2009). Therefore, the use of graphite granule may increase power production and Cr (VI) reduction rate. A two-chamber MFC reactor by Wang et al. (2008) was set up for Cr (VI) reduction using contaminated soil as the inoculum. Chromium reduction in the presence of anaerobic sludge was studied; Cr (VI) (100 mg/L) was completely removed within 48 h of incubation with maximum PD of 767.0 mW/m2 (Xafenias et al., 2015).
2.2 Exploring the Role of MFC in the Removal of Selenite and Nitrate From Wastewater The pollutants generated and released in the environment by the industries have raised concerns globally. Among them the two pollutants selenite and nitrate can be efficiently removed by MFC: Selenite: The glass manufacturing, electrical industries, sewage sludge, fly ash from coalfired power plants, oil refineries, and mining of metal ores (Hamilton, 2004) release effluent which are rich in selenite (SeO3) and selenate (SeO4). The selenite which is disposed is more toxic in nature in comparison to selenate. Selenites easily bioaccumulates in the plants and is toxic to aquatic invertebrates and fishes (Riedel et al., 1991; Hamilton, 2004). Ground water is the major source of drinking water throughout the world, the pollution of which would affect the quantity and the quality of life causing both chronic and acute toxicity. Thus, MFC can be an effective technology for the efficient removal of selenite (Kashiwa et al., 2000; Catal et al., 2008; Rovira et al., 2008). Nitrate: The poultry and agricultural industry has led to increased discharge of nitratebased fertilizers and agro residues in the water bodies (Chebotareva and Nyokong, 1997). This when enters the food chains and the intake by the pregnant females can led to the delivery of child suffering from “blue baby syndrome” and can even be carcinogenic to the humans (Rocca et al., 2007). The use of MFC and reduction of nitrate to nitrite or nitrogen gas occurs at the cathode, researchers have employed a metal catalyst (Polatides and Kyriacou, 2005) or microorganisms as catalysts on cathode electrode (He and Angenent, 2006). In the work by Jiang et al. (2017) an autotrophic denitrifying bacterium was used for the reduction of nitrate or perchlorate with simultaneous electricity generation.
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2.3 Decomposition of Renewable Agricultural Waste by MFC and Simultaneous Electricity Generation The agricultural waste is widely available and can be of various types e.g., the waste generated from farming; poultry processing industries and agroindustries is collectively termed as agrowastes (Chaturvedi and Verma, 2016). They can be effectively used for energy production. However, the lignocellulosic biomass due to the lignin content cannot be directly used for the energy generation. The complex sugar has to be converted to simple sugar for its efficient utilization (Ren et al., 2008; Bhardwaj et al., 2017) e.g., cellulose is used for the generation of electricity via microorganisms which can produce both cellulolytic and exo-electrogenic activities (Rezaei et al., 2009). In a different study by Wang et al. (2014), the hydrosylate of rice straw was used for electricity production. The pentoses present in the agricultural residues is one of the main component of agroresidues, but an effective way for its conversion to bioethanol has not been found yet demanding more. The agrobased industries also release wastewaters that mainly consist of starch or cellulosic components. MFC may be used for the treatment of these carbohydrates polymers before its release to environment. 2.3.1 Starch industrial wastewater (SIW) treatment by MFC The starch industry wastewater consists of the following components: carbohydrates (2300e3500 mg/L) sugars (0.6%e1.2%) protein (0.1%e0.1%) and starch (1500e2600 mg/L) and can be converted to a variety of useful products (Jin et al., 1998). It can be used to generate electricity which would result in the decrease of Chemical Oxygen Demand (COD) (Kim et al., 2004). The MFC can be operated in cycles, Lu et al. (2009) obtained a maximum voltage output and PD in the third cycle out of the four cycles. On the other hand during the production of starch from cassava, high amount of starch-rich wastewater is released, having a very high COD, Biochemical Oxygen Demand (BOD), and total solid (Peters and Ngai, 2000). This starch effluent has high concentration of cyanoglycosides which hydrolyze to form cyanide. Thus, it becomes a necessity to treat the wastewater before it is released into the environment. As most of the treatment steps for the removal of cyanide are expensive the bioremediation via the MFC is an efficient and economically feasible method (Lu et al., 2009). Kaewkannetra et al. (2009) constructed an MFC and utilized cassava wastewater for the generation of electricity and efficiently removed cyanide in the process. On the other hand, it was also observed that the pH has a strong influence on the production of electricity; alkaline pH of 9 increased the power production as observed by Prasertsung et al. (2012).
184 Chapter 9 2.3.2 Cellulose industry wastewater (CIW) treatment via MFC and simultaneous electricity generation Cellulose has also been for generation of electricity via MFC (Niessen et al., 2005). Rismani-Yazidi et al. (2008) employed cellulose for bioelectricity generation using microorganisms from the rumen of cattle. Ren et al. (2008) constructed a dualchambered MFC for electricity generation using cellulose-degrading bacteria Clostridium cellulolyticum and electrochemically active bacteria Geobacter sulfurreducens. Cellulose was also utilized as substrate for electricity generation using a dual-chambered MFC by Sedky et al. (2012). Use of vegetable waste for bioelectricity production was also investigated by Clauwaert et al. (2008). Cellulose from wheat straw; rice mill wastewater, corn stover, and Canna indica can be used to some extent by electrophilc bacteria for electricity generation (Zang et al., 2010). In the study by Toczyłowska-Mami nska et al. (2018) a single-chamber air-cathode MFCs fed cellulose, was used to determine the changes in the bacterial consortium in an MFC fed cellulose over time. It was observed that the Firmicutes sp. was the most predominant bacteria for electron generation. After an extended operation the main genera developed were cellulolytic strains, fermenters and electrogens i.e., Parabacteroides, Proteiniphilum, Catonella and Clostridium.
2.4 Electricity Generation via MFC Using Slaughter House Waste (SHW) Numerous publications have reported the use slaughter house wastewater for generation of electricity (Katuri et al., 2012). SHW contains high amount of proteins, fats and carbohydrates, which is an ideal source for generation of electricity. A dual-chambered MFC consisted of SHW with an inoculum being the anaerobic mixed sludge was constructed. It was observed at a concentration of 900 mg-COD/L maximum PD of 578 mW/m2 was obtained (Katuri et al., 2012). Chaturvedi et al. (2014), studied degradation of chicken feathers by a strain P. aeruginosa with concomitant electricity production in MFC, the maximum voltage of 141 mV was observed after 14 days and the maximum PD and current density of was observed to be 1206.8 mW/m2 and 8.6 mA/m2 respectively.
2.5 Bioremediation of Synthetic Wastewater via MFC and Concurrent Electricity Generation The azo dyes are widely used in textile industries and are one of the major pollutants in wastewaters (Verma and Madamwar, 2005) and can be used as electron acceptors at cathode (Xu et al., 2007). They have the presence of - (eN]Ne) - bond, where the double bond is reduced to hydrazo (A) or amine (B), via the consumption of two or four electrons respectively. The MFC system can be more effective if the dye containing system can
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simultaneously be used for biodegrading organic matter containing wastewater and electricity generation. However, this has only been feasible at laboratory scale and requires further improvisation for its implementation at larger scale. The enzyme laccase was also used at the cathode for the efficient removal of the dye Reactive Blue 221 and simultaneous removal of molasses at the anode (Bakhshian et al., 2011). Liu et al. (2009a,b) reported the production of electricity by employing MFCs using azo dyes as the cathode oxidants and using Klebsiella pneumonia strain L17 in the anode in a dualchamber MFC supplemented with glucose. The results demonstrated that the azo dyes were successfully degraded at the cathode and the power output was dependent on the catholyte pH and the dye molecular structure. Sun et al. (2009) used active Brilliant Red X-3B for dye decolorization, however higher concentration of dye effected the electricity generation from glucose. This was due to the competition between azo dye and the anode for electrons from carbon sources. In an air-cathode single-chambered MFC, equivalent volumes of aerobic and anaerobic sludge were used as inoculum. The MFC was continuously operated at a fixed external resistor of 500 U and voltage for more than 4 months and it was observed that the cathodic potential gradually decreased over time and of the anodic potential remained same. The anaerobic cleavage of azo bond of the Congo red converted it to form aromatic amines in the presence of glucose (Chen et al., 2010; Sun et al., 2011a,b). The bacteria were identified as the members of the genera Azospirillum, Methylobacterium, Rhodobacter, Desulfovibrio, Trichococcus, and Bacteroides in the presence of Congo Red. Venkata Mohan et al. (2008) used synthetic waste in which the redox mediators such as cysteine and sulfur species were present and helped increase the power production by acting as an abiotic electron donor (Aldrovandi et al., 2009) for a short duration of time thus not representing the true performance of the MFC. Recently a new device called Coupled Constructed Wetland MFC (CW-MFC) was constructed to remove recalcitrant dye Reactive Brilliant Red X-3B wastewater and produce energy. It was observed that maximum decolorization rate and the electricity production was 95.6% and 0.852 W/m3, respectively, when the COD was 300 mg/L while the proportion of Reactive Brilliant Red X-3B was 30% (Fang et al., 2015). 2.5.1 Enzyme-mediated MFC: a new approach toward bioremediation The concept of biocathode has gained importance where the use of bacterial or fungal culture can help in the bioremediation and concurrent electricity generation. For the past few years the concept has gained much interest among the researchers and has even led to the use of laccase a p-diphenol: dioxygen oxidoreductase belonging to the family of multicopper proteins for the treatment of synthetic wastewater. As per the study by Wu et al. (2012) Coriolus versicolor was inoculated in the cathodic chamber of MFC and 2,20 Azino-bis(3-ethylbenzothazoline-6-sulfonate) (ABTS) was added as a redox mediator to the catholyte to enable electron transfer between the electrode and laccase. This study showed that the fungal-based biocathode is better than the conventional abiotic cathode,
186 Chapter 9 with as it exhibited approximately seven-order higher PD. In another study Ganoderma laccase with carbon-fiber-brush air-cathode was used to treat molasses wastewater. It was experimentally validated the laccase activity was higher 108 U/L in the presence of 125 mM of CuSO4 on day eight. The addition of crude laccase broth (420 mV) enhanced the MFC performance in terms of electricity generation more in comparison to the filtered broth (300 mV) and the set effectively maintained power generation for 45 days (Lin et al., 2018). Similarly, in the other study by Bakhshian et al. (2011), enzymatic decolorization of dye Reactive Blue 221 was done in dual chamber MFC in the absence of mediator. As the use of mediator would involve an increase in the cost associated with the MFC, mediator less MFC is more preferred over a mediator based MFC. Thus, the biocathode can be effectively used for the removal of the synthetically generated wastewater and bioremediation.
2.6 The Role of MFC in the Treatment of Brewery Wastewater The use of brewery waste has been more preferred as it does not contain ammonia which is present as incase of animal waste, low strength, food derived organic nature and lack of inhibitory substances. Brewery wastewater COD is also 10 times more concentrated than the domestic waste, has high carbohydrate content, and makes it an ideal substrate for MFC (Vijayaraghavan et al., 2006). Feng et al. (2008) used the wastewater with the help of an air cathode and a maximum PD of 528 mW/m2 was achieved with 50 mM phosphate buffer and the wastewater. In this study a comparison between brewery and domestic waste showed that the brewery waste produced less power. This may be attributed due to the difference in conductivities of the wastewater. The study conducted by Lu et al. (2017) determined long term performance by using 20L MFC consisting of brewery waste, results for 325 days indicated that the MFCs can sustain treatment rates for a long-term period and are strong enough to sustain performance even after system disturbances.
2.7 Bioremediation of Landfill Leachates and Municipal Wastewater via MFC The landfill leachates pollutants have adverse effect on the environment. It is a combination of four major pollutants which includes dissolved organic matter, inorganic macro-components, heavy metals, and xenobiotic organic compounds (Kjeldsen et al., 2002). Zhang et al. (2008) constructed an up-flow air-cathode MFC which was operated continuously for 50hr and produced volumetric power of 12.8 W/m3 and CD of 41 A/m3. Later Greenman et al., 2009 constructed an MFC column and showed electricity and simultaneous treatment of landfill leachate, whereas as Ga´lvez et al. (2009) used three chambered MFCs which were fluidically connected in series for instantaneous leachate treatment and electricity generation.
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Similarly, municipal wastewater has also generated much concern, in the study by Liang et al. (2018) the MFC was operated for a year and the volume used was 1000 L, the largest reported volume so far. In this the removal rate of COD was 70%e80% which actually met the pollution of standards for Municipal Wastewater Treatment Plants (MWTP) of China.
3. Limitations, Future Prospects, and Conclusion MFC was initially started with the purpose of utilizing microbes for power generation, but in the short span of time it evolved as a technology and is improving day by day. MFC has evolved as a “boon” not only in the area of energy generation but in the bioremediation of waste as well. The MFC for its efficient utilization in the future, the limitation which exist should be overcome. The reactor design should be modified so that efficient electricity generation at large scale with minimum cost can be implemented beyond laboratory. The low PD needs to be rectified by either isolating new potential microorganisms or through the application of DNA technology. The mediator to be used in MFC should be cheap and widely available. The cathode and the anode surface area have a very important role to play in MFC, hence more research is required which can help in the optimization of the ratio of the surface area of cathode to anode. The biocathode which involves the use of microorganisms and enzyme has to be applied at larger scale as the laccase enzyme used in EBC has a huge potential for bioremediation. A new concept of “living solar cell” proposed by Rosenbaum et al. (2005) where green alga Chlamydomonas reinhardtii produced hydrogen photosynthetically and is oxidized in situ to produce current. The “living solar cell” is an approach to convert solar energy into electric energy through photosynthetic microorganisms (He et al., 2009) or living plants along with bacteria in MFC (Strik et al., 2008). As the initiative is new it requires further study for its effective implementation in the future and commercialization. In last 2 decades MFC is used as an alternative to the conventional wastewater/waste treatment plants where they would help in bioremediation of waste along with electricity generation. Hence, making MFC a selfsustainable and energy efficient alternative to the costly energy consuming processes. However, more work is required in the areas of MFC development and with the advent of new technologies and adaptations; the evolution of MFC from laboratory to commercial scale can occur and thus be “Boon to the Real World”.
Abbreviations BFC BOD CE CEM CIW
Bio-fuel cell Biochemical oxygen demand Coulombic Efficiency Cation exchange membrane Cellulose industry waste
188 Chapter 9 COD CW-MFC EBC ETC GHGE MFC MWTP PD PEM SHW SIW
Chemical oxygen demand Coupled constructed wetland-MFC Enzymatic biofuel cell Electron transport chain Green house gas emission Microbial fuel cell Municipal wastewater treatment plants Power density Proton Exchange Membrane Slaughter House Waste Starch industrial wastewater
Acknowledgements PV is thankful to DBT (Grant No. BT/304/NE/TBP/2012; Grant No. BT/PR7333/PBD/26/373/2012) and KA is thankful to Central University of Rajasthan, Ajmer, India, for providing the financial support.
Competing Interests All the authors declare that they have no competing interests.
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