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Microbial fuel cell: a new approach of wastewater treatment

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MICROBIAL FUEL CELL: A NEW APPROACH OF WASTEWATER<br />

TREATMENT WITH POWER GENERATION<br />

M.M. GHANGREKAR 1 AND V.B. SHINDE 2<br />

ABSTRACT: Application <strong>of</strong> <strong>Microbial</strong> Fuel Cells (MFCs) may represent a completely<br />

<strong>new</strong> <strong>approach</strong> to <strong>wastewater</strong> <strong>treatment</strong> with production <strong>of</strong> sustainable clean energy.<br />

In recent years, researchers have shown that MFCs can be used to produce<br />

electricity from water containing glucose, acetate or lactate. Studies on electricity<br />

generation using organic matter from the <strong>wastewater</strong> as substrate are in progress.<br />

The performance <strong>of</strong> the MFCs as reported in literature with different substrate is<br />

presented in this paper. Under different conditions such as inoculum culture (pure or<br />

mixed), substrate sources, and external loads, the MFCs are reported to produce<br />

power density in the range 0.3 to 3600 mW/m 2 . Performance <strong>of</strong> the laboratory scale<br />

membrane less MFC using synthetic <strong>wastewater</strong> was evaluated for its effectiveness<br />

for organic matter removal and electricity production. It was observed that this<br />

membrane less MFC was capable to give COD reduction greater than 90 percent,<br />

with maximum power production 6.73 mW/m 2 . If power generation in MFC can be<br />

increased, this technology may provide a <strong>new</strong> method to <strong>of</strong>fset <strong>wastewater</strong> <strong>treatment</strong><br />

plant operating costs, with less excess sludge production.<br />

KEYWORDS: <strong>Microbial</strong> Fuel Cell, Wastewater Treatment, Electric power production<br />

INTRODUCTION<br />

The high energy requirement <strong>of</strong> conventional sewage <strong>treatment</strong> systems are<br />

demanding for the alternative <strong>treatment</strong> technology which will be cost effective and<br />

require less energy for its efficient operation. In past two decades, high rate<br />

anaerobic processes are finding increasing application for the <strong>treatment</strong> <strong>of</strong> domestic<br />

as well as industrial <strong>wastewater</strong>s. The major advantages these systems <strong>of</strong>fer over<br />

conventional aerobic <strong>treatment</strong> are no energy requirement for oxygen supply, less<br />

sludge production, and recovery <strong>of</strong> methane gas. While treating sewage, particularly<br />

in small capacity <strong>treatment</strong> plant recovery <strong>of</strong> methane may not be attractive, because<br />

most <strong>of</strong> the methane produced in the reactor is lost through effluent <strong>of</strong> the reactor.<br />

The methane concentration <strong>of</strong> about 16 mg/L (equivalent COD 64 mg/L) is expected<br />

in the effluent <strong>of</strong> the reactor due to high partial pressure <strong>of</strong> methane gas inside the<br />

reactor 1 . Hence, while treating low strength <strong>wastewater</strong> major fraction <strong>of</strong> the<br />

methane gas may be lost through effluents, reducing the energy recovery.<br />

In addition, due to global environmental concerns and energy insecurity, there<br />

is emergent interest to find out sustainable and clean energy source with minimal or<br />

zero use <strong>of</strong> hydrocarbons. Electricity can be produced in different types <strong>of</strong> power<br />

1 Assistant Pr<strong>of</strong>essor, Department <strong>of</strong> Civil Engineering, Indian Institute <strong>of</strong> Technology, Kharagpur – 721302.<br />

India. (Phone No. 03222 – 283440 (O) 283441 (R); E-mail: ghangrekar@civil.iitkgp.ernet.in)<br />

2 M.Tech. (Environmental Engineering & Management) Student. Department <strong>of</strong> Civil Engineering, Indian Institute<br />

<strong>of</strong> Technology, Kharagpur – 721302. India.


plant systems, batteries or <strong>fuel</strong> <strong>cell</strong>s. Bacteria can be used to catalyze the<br />

conversion <strong>of</strong> organic matter into electricity 2,3,4,5,6,7 . Fuel <strong>cell</strong>s that use bacteria are<br />

classified as two different types: bio<strong>fuel</strong> <strong>cell</strong>s that generate electricity from the<br />

addition <strong>of</strong> artificial electron shuttles (mediators) and microbial <strong>fuel</strong> <strong>cell</strong>s (MFCs) that<br />

do not require the addition <strong>of</strong> mediator 8 . Unlike a battery, a <strong>fuel</strong> <strong>cell</strong> does not store<br />

energy. Instead, it converts energy from one form to another (much like an engine)<br />

and will continue to operate as long as <strong>fuel</strong> is fed to it. However, unlike internal<br />

combustion generators, <strong>fuel</strong> <strong>cell</strong>s convert chemical energy directly into electricity<br />

without an intermediate conversion into mechanical power. Fuel <strong>cell</strong>s, if used for<br />

<strong>wastewater</strong> <strong>treatment</strong>, can provide clean energy for people, apart from effective<br />

<strong>treatment</strong> <strong>of</strong> <strong>wastewater</strong>. The benefits <strong>of</strong> using <strong>fuel</strong> <strong>cell</strong>s include: clean, safe, quiet<br />

performance; high energy efficiency; low emissions; and ease in operating.<br />

Bio<strong>fuel</strong> <strong>cell</strong>s use biocatalysts for the conversion <strong>of</strong> chemical energy to<br />

electrical energy. It is a device that directly converts microbial metabolic or enzyme<br />

catalytic energy into electricity by using conventional electrochemical technology 2 .<br />

The biocatalysts participate in the electron transfer chain between the <strong>fuel</strong>-substrate<br />

(organic or inorganic) and the electrode surfaces 9 . That is, microorganisms or redoxenzymes<br />

facilitate the electron transfer between the <strong>fuel</strong> substrate and the electrode<br />

interface, thereby enhancing the <strong>cell</strong> current. It has been shown that, direct electron<br />

transfer from microbial <strong>cell</strong>s to electrodes occurs only at very low efficiency 10 . Most<br />

<strong>of</strong> the redox-enzymes lack in direct electron transfer with conductive supports and a<br />

variety <strong>of</strong> electron mediators (electron relays) are used for electrical contacting <strong>of</strong> the<br />

biocatalysts and the electrode. Since, most microbial <strong>cell</strong>s are electrochemically<br />

inactive; electron transfer from microbial <strong>cell</strong>s to the electrode is facilitated by the<br />

help <strong>of</strong> mediators such as thionine, methyl viologen, humic acid, etc. Enzyme<br />

catalyzed generation <strong>of</strong> NADH (dihydro-nicotinamide adenine dinucleotide) from<br />

alcohol, lactic acid, amino acids, formate or other abundant substrates could provide<br />

the bio-transformations that activate the anodic compartment <strong>of</strong> the <strong>fuel</strong> <strong>cell</strong> 9 .<br />

Theoretically, any organic or inorganic compound or a mixture can serve as a <strong>fuel</strong>,<br />

provided it is oxidized by the appropriate organism, e.g., the reaction for glucose is 11 :<br />

C 6 H 12 O 6 + 6H 2 O 6CO 2 + 24e - + 24 H + ….(1)<br />

Mediator Less MFC<br />

It has recently been shown that certain metal-reducing bacteria, belonging<br />

primarily to the family Geobacteraceae can directly transfer electrons to electrodes


using electrochemically active redox enzymes, such as cytochromes on their outer<br />

membrane 12,13 . These microbial <strong>fuel</strong> <strong>cell</strong>s does not need mediator for electron<br />

transfer to electrodes and are called as mediator less MFCs. Mediator less MFCs<br />

are considered to have more commercial application potential, because mediators<br />

used in Bio<strong>fuel</strong> <strong>cell</strong>s are expensive and can be toxic to the microorganisms 7 .<br />

The schematic diagram <strong>of</strong> mediator less MFC is shown in the Figure 1. In a<br />

MFC, two electrodes (anode and cathode) are placed in water in two compartments<br />

separated by a proton exchange membrane (PEM). Most studies have used<br />

electrodes <strong>of</strong> solid graphite 7 , graphite-felt 14 , carbon cloth 15 and platinum coated<br />

graphite cathode electrode 16 . Microbes in the anode compartment oxidize <strong>fuel</strong><br />

(electron donor) generating electrons and protons. Electrons are transferred to the<br />

cathode compartment through the external circuit, and the protons through the<br />

membrane. Electrons and protons are consumed in the cathode compartment<br />

reducing oxygen to water.<br />

Rate Limiting Steps: (1) Oxidation <strong>of</strong> Fuel, (2) Electron transfer from the microbial <strong>cell</strong>s to the<br />

electrode, (3) Electric load in the circuit, (4) Proton supply into the cathode compartment, (5) Oxygen<br />

supply and reduction at the cathode [Gil et al. 6 ].<br />

Figure 1: Mediator Less <strong>Microbial</strong> Fuel Cell with rate limiting steps<br />

In addition to microorganisms that can transfer electrons to the anode, the<br />

presence <strong>of</strong> other organisms appears to benefit MFC performance. It is reported<br />

that, a mixed culture generated a current that was six fold higher that that generated<br />

by a pure culture 17 . Hence, the microbial communities that develop in the anode<br />

chamber may have a similar function as those found in methanogenic anaerobic<br />

digesters, except that microorganisms that can transfer electrons to the electrode<br />

surface replace methanogens. Rabaey et al. 18 referred to such microbial<br />

communities as adapted anodophilic consortia. Anodophilic bacteria from different


evolutionary lineages from the families <strong>of</strong> Geobacteraceae, Desulfuromonaceae,<br />

Alteromonadaceae, Enterobacteriaceae, Pasteurellaceae, Clostridiaceae,<br />

Aeromonadaceae, and Comamonadaceae were able to transfer electrons to<br />

electrodes 19 . Methanogens also reported to have a capacity to transfer electrons 20 .<br />

Because the power output <strong>of</strong> MFCs is low relative to other types <strong>of</strong> <strong>fuel</strong> <strong>cell</strong>s,<br />

reducing their cost is essential, if power generation using this technology is to be an<br />

economical method <strong>of</strong> energy production. The overall limiting steps to enhance the<br />

power production are showed in the Figure 1. Further research is required to<br />

enhance the power production by overcoming these limitations. The main<br />

disadvantage <strong>of</strong> a two chamber MFC is that the solution cathode must be aerated to<br />

provide oxygen to the cathode 8 . The power output <strong>of</strong> an MFC can be improved by<br />

increasing the efficiency <strong>of</strong> the cathode, e.g. power is increased by adding<br />

ferricyanide to the cathode chamber 21 .<br />

The effects <strong>of</strong> operational conditions <strong>of</strong> a microbial <strong>fuel</strong> <strong>cell</strong> were investigated<br />

and optimized for the best performance <strong>of</strong> a mediator-less microbial <strong>fuel</strong> <strong>cell</strong> by Gil et<br />

al. 6 . The optimal pH reported was 7. The resistance higher than 500 Ω was the ratedetermining<br />

factor by limiting electron flow from anode to cathode. At the resistance<br />

lower than 200 Ω, proton and oxygen supplies to the cathode were limited. For the<br />

construction <strong>of</strong> an efficient microbial <strong>fuel</strong> <strong>cell</strong>, a non-compartmentalized <strong>fuel</strong> <strong>cell</strong> with<br />

an electrode having a high oxygen reducing activity should be developed. Since the<br />

concentration <strong>of</strong> <strong>fuel</strong> determines the amount <strong>of</strong> electricity generation from the <strong>fuel</strong><br />

<strong>cell</strong>, the device can be used as a BOD sensor.<br />

It is possible to design a MFC that does not require the cathodes to be placed<br />

in water. In hydrogen <strong>fuel</strong> <strong>cell</strong>s, the cathode is bonded directly to the PEM so that<br />

oxygen in air can directly react at the electrode 22 . This technique was successfully<br />

used to produce electricity from <strong>wastewater</strong> in a single chamber MFC 15 . However, a<br />

maximum <strong>of</strong> 788 mW/m 2 power density was reported by Park and Zeikus 21 with a<br />

Mn 4+ graphite anode and a direct air Fe 3+ graphite cathode.<br />

Membrane Less MFC<br />

In a meditor less MFC, the membrane separates the anode from the cathode<br />

as in other MFCs, and the membrane functions as an electrolyte that plays the role<br />

<strong>of</strong> an electric insulator and allows protons to move through 16 . However, the use <strong>of</strong><br />

membrane can limit the application <strong>of</strong> MFC to <strong>wastewater</strong> <strong>treatment</strong>. Proton transfer


through the membrane can be a rate limiting factor especially with fouling expected<br />

due to suspended solids and soluble contaminants in a large scale <strong>wastewater</strong><br />

<strong>treatment</strong> process. In addition, membranes are expensive and hence may limit its<br />

application. A membrane-less microbial <strong>fuel</strong> <strong>cell</strong> (ML-MFC) was developed by Jang<br />

et al. 16 and used successfully to enrich electrochemically active microbes that<br />

converted organic contaminants to electricity. The COD removal rate <strong>of</strong> 526.67 g/m 3<br />

day was reported with maximum power production 1.3 mW/m 2 and current density<br />

6.9 mA/m 2 . The design used in the study showed poor cathode reaction allowing a<br />

large quantity <strong>of</strong> oxygen to diffuse toward the anode. Further studies are required to<br />

improve the design <strong>of</strong> ML-MFC to improve current yield and COD removal efficiency.<br />

Power production <strong>of</strong> MFC and Further Development Required<br />

The major limitations to implementation <strong>of</strong> MFCs for <strong>treatment</strong> <strong>of</strong> <strong>wastewater</strong><br />

are their power density is still relatively low and the technology is only in the<br />

laboratory phase. Based on the potential difference, ∆E, between the electron donor<br />

and acceptor, a maximum potential <strong>of</strong> nearly 1 V can be expected in MFCs, which is<br />

not much greater than the 0.7 V that is currently being produced 21 . However, by<br />

linking several MFCs together, the voltage can be increased. Current and power<br />

densities are lower than what is theoretically possible, and system performance<br />

varies considerably as shown in Table 1. The maximum power density reported in<br />

the literature, 3600 mW/m 2 , was observed in a dual-chamber <strong>fuel</strong> <strong>cell</strong> treating<br />

glucose with an adapted anaerobic consortium in the anode chamber and a<br />

continuously aerated cathode chamber containing an electrolyte solution that was<br />

formulated to improve oxygen transfer to cathode 18 .<br />

Cost <strong>of</strong> the MFC can be minimized by using plain graphite electrodes without<br />

exogenous electron shuttles and a commercially available membrane 19 . Further<br />

improvement in the power density is required, and the rates <strong>of</strong> electron transfer to<br />

the anode are the major limiting factor. Optimization <strong>of</strong> MFCs is required, which<br />

involves investigation <strong>of</strong> a variety <strong>of</strong> aspects such as, anodophilic consortium<br />

selection for efficient electron transfer to electrode; cathode performance, oxygen<br />

supply and oxidation <strong>of</strong> <strong>fuel</strong>; MFC configuration, external resistance and electrodes<br />

(material and surface area); specific inoculum and concentration <strong>of</strong> bacteria; types <strong>of</strong><br />

organic material in the <strong>wastewater</strong>, and electron shuttles.


TABLE 1: POWER GENERATION RATES REPORTED IN THE LITERATURE 8<br />

Substrate Description Power (mW/m 2 )<br />

Complex Anaerobic sediments 16<br />

Starch <strong>wastewater</strong> 19<br />

Starch <strong>wastewater</strong> 20<br />

Domestic Wastewater 24<br />

Anaerobic sediments 28<br />

Domestic <strong>wastewater</strong>, CE-PEM 28<br />

Domestic <strong>wastewater</strong>, CE no PEM 146<br />

Defined Lactate 0.6 – 15<br />

Lactate, Peptone, and yeast extract 788<br />

Acetate (salt Bridge) 0.3<br />

Acetate 14 - 49<br />

Glucose 33 – 3600<br />

Glucose – CE-PEM 262<br />

Glucose – CE (no PEM) 494<br />

The basic disadvantages <strong>of</strong> microbial <strong>fuel</strong> <strong>cell</strong>s are their generally low<br />

coulombic yields and low power outputs. Many more improvements will be<br />

necessary, before biological <strong>fuel</strong> <strong>cell</strong> production and use can be commercialized. A<br />

membrane less MFC could improve the economic feasibility <strong>of</strong> the process to treat<br />

<strong>wastewater</strong> by reducing not only the capital investment, by eliminating costly<br />

membrane, but also the operational cost for the membrane maintenance. The<br />

objective <strong>of</strong> this study was to evaluate the electricity production potential and<br />

<strong>treatment</strong> efficiency <strong>of</strong> mediator less microbial <strong>fuel</strong> <strong>cell</strong> without membrane, using<br />

synthetic <strong>wastewater</strong> and mixed anaerobic microbial culture as inoculum.<br />

MATERIAL AND METHODS<br />

Membrane-less microbial <strong>fuel</strong> <strong>cell</strong><br />

Figure 2 shows the schematic diagram <strong>of</strong> the membrane-less microbial <strong>fuel</strong><br />

<strong>cell</strong> (ML-MFC) used in this study. The anode was at the bottom, and the cathode at<br />

the top <strong>of</strong> cylinder-shaped reactor made <strong>of</strong> polyacrylic having internal diameter <strong>of</strong> 10<br />

cm. Glass wool (4 cm depth) and glass bead (4 cm depth) was placed at the upper<br />

portion <strong>of</strong> the anode. Graphite rod, as roll form, was used for both anode and<br />

cathode. Total height <strong>of</strong> the reactor was 60 cm, and distance between the anode<br />

and cathode was 20 cm, including glass wool and glass bead. The apparent surface<br />

area <strong>of</strong> each anode and cathode was 46.65 cm 2 . The <strong>fuel</strong> was supplied to the bottom<br />

<strong>of</strong> the anode and the effluent left through the cathode compartment at the top. The<br />

electrodes were connected with copper wire through a resistance ranging from 10 Ω


to 100 Ω, including the resistance <strong>of</strong> copper wire and a multimeter. The internal<br />

resistance <strong>of</strong> the MFC was ranging from 3 MΩ to 4.5 MΩ.<br />

Figure 2: Membrane Less <strong>Microbial</strong> Fuel Cell used in the study<br />

Wastewater<br />

The <strong>wastewater</strong> was applied at the rate <strong>of</strong> 5.011 L/d making hydraulic<br />

retention time (HRT) in the MFC <strong>of</strong> 24 h. The cathode compartment was aerated at<br />

rate <strong>of</strong> 60 mL/min for the cathode reaction. A synthetic sewage containing sucrose<br />

as a carbon source was used throughout the study. The composition <strong>of</strong> the synthetic<br />

<strong>wastewater</strong> used is provided in Table 2. The COD <strong>of</strong> synthetic <strong>wastewater</strong> used was<br />

in the range 312 to 446 mg/l and influent pH was maintained in the range 7.2 to 7.6.<br />

TABLE 2: THE COMPOSITION OF THE SYNTHETIC WASTEWATER<br />

Component Sucrose NaHCO 3 NH 4 Cl K 2 HPO 4 KH 2 PO 4 CaCl 2 .2H 2 O MgSO 4 .7H 2 O<br />

mg/ L 300-450 480 95.5 10.5 5.25 63.1 19.2<br />

Note: Trace metals were added as FeSO 4 .7H 2 O = 10 mg/L, NiSO 4 .6H 2 O = 0.526 mg/l,<br />

MnSO 4 .H 2 O = 0.526 mg/l, ZnSO 4 .7H 2 O = 0.106 mg/l, H 3 BO 3 = 0.106 mg/l, CoCl 2 .6H 2 O = 52.6<br />

µg/L, CuSO 4 .5H 2 O = 4.5 µg/L, and (NH 4 ) 6 Mo 7 O 24 .4H 2 O = 52.6 µg/L.<br />

Enrichment <strong>of</strong> electrochemically active microbes for operating MFC<br />

The ML-MFC was inoculated with sludge (1.0 L) collected from septic tank<br />

bottom. All experiments were conducted at room temperature ranging from 29 to<br />

33 o C. For the first fifteen days <strong>of</strong> operation the MFC was operated without any<br />

pre<strong>treatment</strong> <strong>of</strong> the inoculum sludge. After fifteen days, the sludge form the MFC<br />

was removed, heated and inoculated. The sludge was heated at 100 o C for 15<br />

minutes to suppress the methanogens, cooled at room temperature and 1 L volume<br />

<strong>of</strong> sludge was added to the reactor in the anode compartment. No microbial addition<br />

was carried out in cathode compartment in both the cases.


Analyses<br />

The potential was measured using a digital multimeter (MASTECH M-830B,<br />

Russia) and converted to power according to P= iV, where P = power (W), i = current<br />

(A), and V = voltage (V). The influent and effluent characteristics such as, COD, pH,<br />

dissolve oxygen (DO), were monitored according to Standard Methods 23 .<br />

Biochemical oxygen demand (BOD) was determined for three days at 27 o C.<br />

RESULT AND DISCUSSION<br />

Enrichment<br />

The ML-MFC, inoculated with septic tank sludge, was operated on batch<br />

mode for first four days and from fifth day onward with continuous mode. The electric<br />

current production <strong>of</strong> 0.3 mA was observed at external load <strong>of</strong> 10 Ω for first five days<br />

<strong>of</strong> continuous operation, but latter gradual decrease in current production was<br />

observed and it was 0.1 mA after 15 days. This decrease could be attributed to the<br />

growth <strong>of</strong> methanogens in the anode chamber, reducing the availability <strong>of</strong> electron<br />

and proton, hence reducing current. The sludge from the anode chamber <strong>of</strong> MFC<br />

was heated at 100 ºC and re-inoculated. This method was found effective to obtain<br />

an enriched culture <strong>of</strong> hydrogen producers 24 . The current slowly increased for the<br />

first week, and it was 0.1 mA at external load <strong>of</strong> 100 Ω. The maximum current <strong>of</strong><br />

0.175 mA was observed at external load <strong>of</strong> 10 Ω with voltage 0.19 V. The open<br />

circuit potential was about 0.3 V after fifteen days <strong>of</strong> operation. Power density <strong>of</strong> 6.73<br />

mW/m 2 was observed in this experiment which is higher than the value 1.3 mW/m 2<br />

reported earlier 16 .<br />

COD Removal Efficiency<br />

The ML-MFC was operated at four different external resistance (10 to 100 Ω)<br />

and influent COD concentration ranging from 312 mg/l to 446 mg/l as presented in<br />

Table 3 and Figure 3. After 55 days <strong>of</strong> operation the COD and BOD removal<br />

efficiency <strong>of</strong> ML-MFC was 90.86% and 90.67%, respectively. The steady state<br />

condition for COD removal efficiency was observed after 55 days <strong>of</strong> operation with<br />

COD removal capacity <strong>of</strong> 0.406 kg/m 3 .d. The specific organic removal rate, with<br />

respect to anode chamber, <strong>of</strong> 0.08 kg COD/ kg VSS.d was observed. Studies are in<br />

progress to increase the loading capacity. The COD removal in the anode<br />

compartment was 46.36%. After achieving steady state, the effluent COD was 40.8<br />

mg/l and BOD 3 at 27 o C was 25 mg/L. These values demonstrate the capacity <strong>of</strong> ML-


MFC for <strong>wastewater</strong> <strong>treatment</strong>. The COD and BOD values reported are for unsettled<br />

effluent containing SS and VSS concentration <strong>of</strong> 40 mg/L and 6.2 mg/L, respectively.<br />

Further improvement in the effluent quality is expected by employing settling tank<br />

after MFC. The COD removal efficiency observed is on the higher side <strong>of</strong> the<br />

maximum efficiency reported in literature as 80 to 90 percent 15,16 . However, the<br />

organic loading rate as high as 27.02 kg COD/m 3 .d is reported with specific organic<br />

load as 18.63 kg glucose/ kg VSS.d for hydrogen production in CSTR type reactor 25 .<br />

TABLE 3: PERFORMANCE OF THE MEMBRANE LESS MICROBIAL FULE CELL<br />

A] COD AND BOD REMOVAL<br />

Days External<br />

Resistance<br />

(Ω)<br />

COD<br />

(Inlet)<br />

(mg/L)<br />

0-15 100 329.17<br />

(±45.43)<br />

16-35 10 399.90<br />

(±34.33)<br />

36-55 25 312.33<br />

(±16.74)<br />

56-78 50 446.50<br />

(±36.08)<br />

COD<br />

(middle)<br />

(mg/L)<br />

248.50<br />

(±19.09)<br />

312.30<br />

(±22.60)<br />

208.17<br />

(±55.53)<br />

239.50<br />

(±17.67)<br />

B] ELECTRICITY PRODUCTION<br />

COD<br />

(outlet)<br />

(mg/L)<br />

162.50<br />

(±24.74)<br />

72.4<br />

(±20.90)<br />

56.30<br />

(±11)<br />

40.8<br />

(±3.26)<br />

Efficiency<br />

(%)<br />

50.63<br />

BOD<br />

(Inlet)<br />

(mg/L)<br />

BOD<br />

(middle)<br />

(mg/L)<br />

BOD<br />

(outlet)<br />

(mg/L)<br />

DO<br />

(Inlet)<br />

(mg/L)<br />

DO<br />

(outlet)<br />

(mg/L)<br />

------ ------ ----- ----- ------<br />

81.89 280 175 48 5.4 4.33<br />

(±15) (±10) (±5) (±1.0) (±0.25)<br />

81.97 240 158 35 5.5 3.75<br />

(±20) (±12) (±5) (±1.0) (±0.35)<br />

90.86 268 162 25 5.4 4.14<br />

(±18) (±13) (±5) (±1.0) (±0.39)<br />

Days Current<br />

(mA)<br />

0-15 0.091<br />

(±0.011)<br />

16-35 0.175<br />

(±0.007)<br />

36-55 0.148<br />

(±0.007)<br />

56-78 0.121<br />

(±0.008)<br />

Voltage<br />

(V)<br />

0.116<br />

(±0.007)<br />

0.188<br />

(±0.003)<br />

0.175<br />

(±0.007)<br />

0.151<br />

(±0.005)<br />

Resistance Power<br />

(ohm) (mW/m 2 )<br />

100 2.29<br />

(±0.39)<br />

10 6.73<br />

(±0.44)<br />

25 5.46<br />

(±0.39)<br />

50 3.96<br />

(±0.46)<br />

Jule<br />

(J/d)<br />

HRT<br />

(hrs)<br />

0.92 24<br />

2.72 24<br />

2.20 24<br />

1.597 24<br />

Effect <strong>of</strong> External Resistance<br />

It was observed that at lower external resistance the current production is<br />

higher and vice versa. Even for same <strong>wastewater</strong> COD concentration the production<br />

<strong>of</strong> current is decreases due to increase in resistance shown in Figure 3. At same<br />

COD concentration when resistance was increased to 25 Ω and 50 Ω, the production<br />

<strong>of</strong> current decreased to 0.148 mA and 0.121 mA, respectively. These results show<br />

that the resistance becomes the rate-limiting step (step 3 in Figure 1). Even at lower<br />

resistance, low current production could be attributed to the lower electron<br />

consumption rate at the cathode than transfer rate from the external circuit. This<br />

might be due to limited supply <strong>of</strong> proton or oxygen (steps 4 and 5 in Figure 1). The


lower current production means that some electrons are consumed by mechanism(s)<br />

other than the cathode reaction. At this point it is not known how this is possible. It is<br />

plausible that under the conditions <strong>of</strong> limited electron disposal through the circuit with<br />

a high resistance, the electrons are consumed in the anode to reduce other electron<br />

acceptors such as sulfate and nitrate 6 , or oxygen diffused from cathode compartment<br />

or dissolved oxygen present in the influent. At low resistance the electrons move<br />

more easily through the external circuit than at high resistance, oxidizing electron<br />

carriers <strong>of</strong> the microbes in the anode. Higher <strong>fuel</strong> oxidation by the microbes is<br />

expected with high ratio <strong>of</strong> oxidized electron carriers <strong>of</strong> the culture at a low<br />

resistance to remove organic contaminants at a high rate 16 .<br />

Influent COD, mg/L<br />

COD at outlet <strong>of</strong> anode chamber, mg/L<br />

0.25<br />

600<br />

Efflent COD, mg/L<br />

Current,mA<br />

Resistance, Ohm<br />

Voltage, V<br />

0.23<br />

COD (mg/L) & Resistance (ohm)<br />

500<br />

400<br />

300<br />

200<br />

100<br />

0.21<br />

0.19<br />

0.17<br />

0.15<br />

0.13<br />

0.11<br />

0.09<br />

0.07<br />

Current (mA), Voltage (V)<br />

0<br />

0.05<br />

0 20 40 60 80<br />

Time (days)<br />

Figure 3. Time course <strong>of</strong> performance <strong>of</strong> membrane less microbial <strong>fuel</strong> <strong>cell</strong><br />

Effect <strong>of</strong> Dissolved oxygen monitoring <strong>of</strong> cathode compartment<br />

The microbial <strong>cell</strong> was operated with aeration in the cathode compartment.<br />

The current and DO concentration measured under different external load are<br />

provided in Table 3. When the cathode compartment was aerated, the current<br />

increased sharply, and so did DO slowly. When the aeration was stopped the current<br />

decreased, whilst the decrease in DO was less significant. These results show that<br />

DO is the major limiting factor for the operation <strong>of</strong> a microbial <strong>fuel</strong> <strong>cell</strong> with graphite<br />

electrode. Probably, due to poor catalytic activity <strong>of</strong> graphite to reduce oxygen, which<br />

can be explained better by analyzing proton compensation in cathode chamber 6 .


CONCLUSIONS<br />

Under present investigation, the membrane less MFC was used effectively for<br />

synthetic <strong>wastewater</strong> <strong>treatment</strong> with COD and BOD removal about 90%. The power<br />

production <strong>of</strong> this MFC observed was 6.73 mW/m 2 . If power generation in these<br />

systems can be increased, MFC technology may provide a <strong>new</strong> method to <strong>of</strong>fset<br />

<strong>wastewater</strong> <strong>treatment</strong> plant operating cost, making <strong>wastewater</strong> <strong>treatment</strong> more<br />

affordable for developing and developed nations. The possibility <strong>of</strong> direct conversion<br />

<strong>of</strong> organic material in <strong>wastewater</strong> to bio-electricity is exciting, but fundamental<br />

understanding <strong>of</strong> the microbiology and further development <strong>of</strong> technology is required.<br />

With continuous improvements in microbial <strong>fuel</strong> <strong>cell</strong>, it may be possible to<br />

increase power generation rates and lower their production and operating cost.<br />

Thus, the combination <strong>of</strong> <strong>wastewater</strong> <strong>treatment</strong> along with electricity production may<br />

help in saving <strong>of</strong> millions <strong>of</strong> rupees as a cost <strong>of</strong> <strong>wastewater</strong> <strong>treatment</strong> at present.<br />

ACKNOWLEDGEMENT<br />

The grants provided by University Grants Commission, New Delhi (F. No. 14-10/2003 (SR)) under the<br />

head Major Research Project, to undertake this research work, are duly acknowledged.<br />

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