International Journal of Energy and Environmental Engineering
International Journal of Energy and Environmental Engineering
International Journal of Energy and Environmental Engineering
Full Title: Performance of pilot-scale microbial fuel cells treating wastewater with associated
bioenergy production in the Caribbean context
Abstract: Microbial fuel cell (MFC) technology represents a form of renewable energy that
generates bioelectricity from what would otherwise be considered a waste stream.
MFCs may be ideally suited to the small island developing state (SIDS) context, such
as Trinidad and Tobago where seawater as the main electrolyte is readily available
and economical renewable and sustainable electricity is also deemed a priority. Hence
this project tested two identical laboratory-scaled MFC systems that were specifically
designed and developed for the Caribbean regional context. They consisted of two
separate chambers, an anaerobic anodic chamber inoculated with wastewater and an
aerobic cathodic chamber separated by a proton exchange membrane. Domestic
wastewater from two various wastewater treatment plants inflow (after screening) was
placed into the anodic chamber, and seawater from the Atlantic Ocean and Gulf of
Paria placed into the cathodic chambers respectively with the bacteria present in the
wastewater attaching to the anode. Experimental results demonstrated that the
bacterial degradation of the wastewaters as substrate induced an electron flow through
the electrodes producing bioelectricity whilst simultaneously reducing the organic
matter as biochemical oxygen demand and chemical oxygen demand by 30 to 75%.
The average bioenergy output for both systems was 84 mW/m² and 96 mW/m²
respectively. This study demonstrated the potential for simultaneous bioenergy
production and wastewater treatment in the SIDS context.
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Bioelectricity energy
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7 Waste Oxygen Seawater
Oxygen
8 water deficit as
A excess C
9 substrate Catholyte
10 N A
11 O T
12 CH3COO3
13 D H
14 E O2 O
15 H+ H+ D
16 E
CO2 H2O
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20 Proton exchange
Biofilm
21 membrane
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23 Figure 1. Schematic of Microbial Fuel Cell based on Direct Bioelectrocatalysis (adapted after [6]).
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27 The microbes in a MFC may gain all the energy and carbon required for cellular growth from the
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29 oxidation of the complex organic material and as such MFC technology has been considered self-
30 sustaining [7]. In other words as long as conditions remain favourable for current production, a MFC
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32 system has the potential to produce electricity indefinitely.
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35 2. Background theory - Microbial fuel cell technology for simultaneous energy generation and
36 biological wastewater treatment
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39 To assess bioelectricity generation from microbes, metabolic pathways governing microbial electron
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41 and proton flows must be determined. Typical electrode reactions within MFCs are shown in
42 Equations 1 and 2 [7, 8].
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45 Anodic reaction: CH3COO + 2H2O microbes⟶ 2CO2 + 7H+ + 8e- (1)
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47 Cathodic reaction: O2 + 4e− + 4H+→2H2O (2)
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50 Microbes in the anodic chamber of a MFC oxidize any added substrates and generate electrons and
51 protons in the process. Carbon dioxide is produced as an oxidation byproduct. The electrons (e-) are
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53 absorbed by the anode and transported to the cathode through an external circuit. After crossing the
54 proton exchange membrane (PEM) or a salt bridge (Figure 1), the protons enter the cathodic chamber
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56 where they combine with oxygen to form water (Equation 2). Microbes in the anodic zone extract
57 electrons and protons in a dissimilative process of oxidizing organic substrates. Bioelectricity
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59 generation occurs by keeping microbes separated from oxygen (i.e. under anaerobic conditions) or via
60 end terminal acceptors other than the anode. This requires an anaerobic anodic chamber. Many
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62 microorganisms possess the ability to transfer electrons derived from the metabolism of organic matter
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to the anode. Wastewater and sludge produced from water and wastewater treatment processes are all
1 rich sources for these specific microorganisms. The ideal performance of a MFC depends on the
2 electrochemical reactions that occur between the organic substrate at a low potential such as with
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4 wastewater and the final electron acceptor having a high potential such as with oxygen. However, its
5 ideal cell voltage is uncertain because the electrons are transferred to the anode from the organic
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7 substrate through a complex respiratory chain that varies from microbe to microbe and even for the
8 same microbe when growth conditions differ. Nevertheless, the actual cell potential is always lower
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10 than its equilibrium potential because of irreversible losses in any system [7, 8].
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3. Materials and method
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Figure 2 illustrates the configurations of the two identical MFCs used in this study that consisted of an
16 anode, cathode, the PEM, and a multimeter that measures voltage and current across the unit. Air
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pumps were connected to the cathodic chamber of the fuel cell. The MFCs used graphite for both
19 electrodes and the PEM used was a Nafion ion exchange membrane.
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43 Figure 2. Experimental configuration of microbial fuel cells used at laboratory pilot-scale (adapted after [3])
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47 Most MFCs have a PEM that separates the anodic and cathodic chambers and acts as a barrier to
48 oxygen, but allows protons (i.e. H+ ions) to pass through and be delivered from the anode to the
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50 cathode cell. Thus a typical two-chamber MFC consists of an anode and cathode that are placed in
51 separate cells/chambers partitioned by a PEM. The anode is supplied with influent wastewater that
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53 contains the microorganisms required for the bioelectrocatalysis process [8]. The graphite anode
54 oxidises the substrate producing protons of hydrogen and an effluent of carbon dioxide.
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56 Simultaneously the graphite cathode receives the protons through the PEM, while reducing the oxygen
57 present in this saltwater chamber that is supplied by an external air pump. Two MFC devices were
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59 constructed with one using seawater from the Atlantic Ocean and the second system using seawater
60 from the Gulf of Paria. Both MFCs contained the same Nafion PEM and graphite electrodes, and were
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62 of the same size and scale to allow comparison of results.
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1 Full-strength domestic wastewater was collected as influent once per week from two of the Trinidad
2 and Tobago Water and Sewerage Authority’s (WASA) municipal wastewater treatment plants
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4 (WWTPs) whose characteristics are depicted in Table 1. The wastewater used as inoculum into the
5 MFCs had no modifications made such as pH adjustment, addition of nutrients, or even dilution. The
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7 entire setup was left for one hour for stabilisation to occur, and the reading of the multimeter was noted
8 down twice daily for a maximum of twelve days when wastewater would be exchanged.
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12 Table 1. Characteristics of Domestic Wastewater Treatment Plants (WWTPs) from the Water and Sewerage Authority
13 (WASA), Trinidad (October 2012 to July 2013)
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15 Characteristics Unit WWTP (A) WWTP (B)
16 pH _ 7.83 7.89
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18 Total solids mg/l 1140 1856
19 Total dissolved solids mg/l 980 974
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21 BOD5 mg/l 260 192
22 COD mg/l 954 878
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24 Chlorides mg/l 262 232
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27 Regular water quality analysis was completed for the wastewater influent into the MFC and for the
28 treated outflow from October 2012 to August 2013 including the measurement of pH, temperature,
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30 suspended solids, ammonia, nitrites, nitrates, phosphates, chlorides, chemical oxygen demand (COD)
31 and biochemical oxygen demand (BOD). The concentrations of ammonia, nitrite, nitrate,
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33 orthophosphate, COD, and suspended solids were determined using a Hach Lange DR 2800
34 spectrophotometer according to United Stated Environment Protections Agency approved standards
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36 for wastewater analysis [9, 10].
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39 Water sample temperature and pH were measured immediately after collecting the samples (i.e. from
40 influent and effluent) with model WTW Var meter handheld pH/mV/Temperature meter manufactured
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42 by Wissenschaftlich-Technische Werkstätten GmbH, Weilheim Germany.
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45 COD was measured using Hach's USEPA-approved dichromate COD Method [9,10]. Globally it is
46 one of the most widely used methods as it allows easy process monitoring and reporting of wastewater
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48 samples. The Hach Lange DRB200 Reactor (Heating block) is preheated to 150 °C. 100 ml of inflow
49 and outflow water samples are mixed for 30 seconds. Thereafter 2.0 ml are pipetted into a vial. The
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51 vial is inverted gently several times and placed into the DRB200 reactor to be heated for
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approximately two hours. Next the sample is cooled for 20 minutes to approximately 120 °C or less.
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54 The outside of the vial is cleaned with ethanol using a tissue and then inserted into the
55 spectrophotometer whereby the instrument reads the barcode and results are coded as mg/l of COD.
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The biochemical oxygen demand (BOD5) was determined using the OxiTOP IS 12-6 system supplied
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60 by WTW (Wissenschaftlich-Technische-Werkstatten GmbG, Wielheim, Germany). The system uses a
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piezo-resistive measure of pressure differences from a respirometric method based on carbon dioxide
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produced within the bottle. A nutrient inhibitor was added to suppress the oxidation of ammonia to
1 nitrates/nitrites (i.e. nitrification inhibitor N-Allylthiourera). The pressure changes when sodium
2 hydroxide transforms into sodium carbonate. Generated carbon dioxide is then removed by adding
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4 sodium hydroxide tablets. The pressure changes are recorded by an electronic data logger and
5 measured over a five-day period at a constant temperature of 20°C. The water sample volume used
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7 was approximately 0.5 litres for the influent and effluents respectively. After 30 minutes of aeration by
8 air pumps, a nutrient inhibitor was added to the samples, and bottles were incubated at a constant
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10 temperature for five days. This method proved to be simple to operate, allowed improved
11 controllability and non-toxicity of samples, and had a broad measurement range up to 4000 mg/l BOD.
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13 Since the measured pressure is automatically converted, the values can be directly read as mg/l BOD.
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15 4. Results and discussion
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18 Both of the dual chambered MFC units were run in parallel and simultaneously. The MFCs were
19 operated by separately feeding domestic wastewater with similar but fluctuating concentrations. The
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21 effects of wastewater concentrations on COD, BOD and ammonia-nitrogen removal efficiency and
22 current generation was observed.
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46 Figure 3. Mean Chemical oxygen demand (mg/l), Ammonium-Nitrogen (NH4-N, mg/l), and Biochemical oxygen demand
47 (mg/l) with standard deviations for influent and effluent for both MFC units (October 2012 to August 2013, sample number
48 = 90).
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51 Figure 3 shows the water quality analysis results for both MFC units. In terms of the mean COD
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53 inflow and outflow values, it can be clearly seen that on average a 50% reduction in COD is achieved
54 consistently for both units. Thus these early results indicate that even with weakly loaded systems, a
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56 MFC system has great potential as a wastewater treatment process since organic loadings of COD can
57 be easily converted into electricity with a concomitant reduction of excess sludge production.
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60 Ammonia removal was consistent and occurred for both MFC systems. Figure 3 also presents the
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62 mean inflow and outflow of ammonium ion concentrations and shows average decreasing
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concentrations of approximately 50% for this weakly loaded system. Ammoniacal-nitrogen (NH4-N)
1 as a nutrient is another key wastewater quality parameter. This determinant is used to efficiently
2 control water and wastewater treatment processes and to demonstrate compliance to EMA imposed
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4 discharge consents in the Trinidad and Tobago situation. It can also be used to indicate the presence of
5 untreated sewage at points of abstraction and infer associated risk from pathogens. As can be seen the
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7 mean removal efficiency for MFC 1 was only very slightly greater than that of MFC 2.
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10 Again in Figure 3, the mean inflow and outflow BOD concentration was determined and showed
11 average decreasing concentrations of approximately 50% for both MFCs, with MFC 2 performing the
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13 best. In fact a linear correlation existed between the strength of the influent organic matter as BOD in
14 the wastewater and the energy yielded from both MFCs since the bacteria adhering to the anode
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16 surface degrade organic matter under anaerobic conditions using bacterial growth and decay kinetics
17 (e.g. Monod reactions). As a consequence of the degradation reaction, carbon dioxide, protons and
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19 electrons were produced [5,11]. The electrons flow through the circuit and the protons pass through the
20 salt-bridge (i.e. the PEM) that is attached to the cathode. The protons and electrons react with oxygen
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22 on the cathode and become water molecules thereby diluting the seawater to brine [12]. Since the
23 influent BOD ranged from 150 to 300 mg/l (i.e. a weak domestic sewage) and as both MFCs showed
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25 an average removal rate ranging from 40 to 60 % respectively, it can be inferred that a typical normal
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sewage strength as influent ranging from 300 to 600 mg/l would achieve improved BOD removal rates
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28 with subsequent higher levels of bioelectricity generated due to greater electron transfer to the anode.
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31 The variation in the pH of the inflow conditions and outflow conditions was also measured and is
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33 shown in Table 2. As is apparent and as is expected, there is a mean drop in pH from slightly alkaline
34 conditions down to neutral conditions as the nutrient load is exhausted.
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37 Table 2. Mean pH values and standard deviations for inflow and both MFC units from October 2012 to July 2013.
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39 Direction of Flow Mean pH (90 samples) Standard deviation of range
40 Inflow 7.83 0.21
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42 Outflow MFC 1 6.97 0.53
43 Outflow MFC 2 6.84 0.41
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22 Figure 4. Mean monthly power generated (mW/m2) for both microbial fuel cells (MFCs) from October 2012 to July 2013.
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25 Figure 4 illustrates the mean monthly power produced from the two identical MFC units. The
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27 fluctuation of the power generated is a direct relation to the presence and behaviour of microorganisms
28 and the associated electron flow across the fuel cells. In general and as anticipated a higher bioenergy
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30 production was recorded for higher BOD and COD loadings, although localised microbial community
31 variations in individual cells does seem to have a greater impact. The average monthly power output
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33 for MFC 1 ranged from 27.2 to 115.8 mW/m2 with an overall mean power output of 84 mW/m2 whilst
34 MFC 2 ranged from 26.2 to 175.9 mW/m2 for power generation monthly with an overall average of 96
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36 mW/m².
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58 Figure 5. Daily electric current (mA) generation for both MFCs treating domestic wastewater from October 2012 to
59 January 2014 (Sample number, n=90).
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Coulombic efficiency and power output for MFCs have been reviewed by several authors such as Lee
1 et al. [13], Niessen et al. [14], Pant et al. [15], and Zuo et al. [16]. In summary, they found that
2 domestic wastewater at a chemical organic loading strength of 600 mg/l had a mean current density of
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4 0.06 mA/cm2, whilst brewery wastewater with an organic strength of 2240 mg/l had a corresponding
5 average current density of 0.2 mA/cm2. The current generation for MFC 1 and MFC 2 is illustrated in
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7 Figure 5. Both MFC 1 and MFC 2 were batch fed with wastewater samples at similar conditions in
8 order to support the formation of biomass and subsequent electricity. The MFCs were continuously
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10 monitored during the entire experimental period and readings were logged at the end of each twenty
11 four period with the inoculation time being considered as time zero. The readings were noted down for
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13 90 days of MFC operation. Higher bioelectricity generation can be as a result of more abundant
14 electron acceptors (i.e. oxygen availability). The full strength wastewater used in the anodic chambers
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16 showed that the current gradually increased for a few days, and then there was a decline in electric
17 current production. The range of current produced was 0.1 to 0.67 mA respectively with variations in
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19 current (mA) generation due to the availability of less oxidisable substrates within the wastewater
20 samples.
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23 The difference in power generation for identical MFC units illustrates the bioelectricity generated was
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25 directly proportional to both the variability in wastewater inflow quality and the salt-content of the
26 seawater source used. Furthermore, small differences in lab-scale system setup can considerably
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28 influence energy production rates although the substrate degradation rates were not greatly impacted
29 upon. For a large-scale MFC setup this situation may not arise since economies-of-scale issues may
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31 mean localised biofilm fouling may be regularised on the anode and especially on the PEM as it
32 dictates proton passage.
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36 5. Conclusions and future outlook
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39 Experimental results of this research demonstrated that the bacteria present in two various sources of
40 domestic wastewater allowed for an electron flow through the electrodes producing bioelectricity and
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42 subsequently reduced 30-80% of organic matter (as BOD and COD) present. The MFC technology has
43 shown to be a viable technology at laboratory scale for treating urban wastewater of varying strengths
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45 and produced a constant but variable production of bioenergy for the SIDS context. The project
46 expands the knowledge of existing technologies in the hopes of improving and optimising water
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48 consumption, treatment and energy generation and usage in the Caribbean region. Performance of the
49 two chamber MFC system demonstrated its effectiveness for simultaneous wastewater treatment and
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51 bioelectricity production. It is envisaged that future developments of MFCs can lead to more promising
52 results and the technology eventually made feasible for combined large-scale wastewater treatment and
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54 sustainable energy generation.
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57 Follow-on research should focus on two main areas:
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60 Optimisation of the bioelectricity energy generation mechanism so that the wastewater
61 treatment process can be largely self-sustaining. This would mean comparing the typical energy
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needs of traditional wastewater treatment processes in the Caribbean region using typical
1 municipal and industrial waste streams with possible MFC bioelectricity generation setups to
2 ascertain if a zero-energy system could be eventually developed.
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5 Measuring microbial species diversity and biofilm make-up on the anode and PEM to ascertain
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7 their impact, if any, on bioelectricity generation rates and simultaneous organic substrate
8 removal rates.
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11 Using the abundance of solar energy in the Caribbean SIDS scenario to pre-heat the wastewater
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13 influent via simple glass tubes coupled with aluminium reflector solar collector/heat exchanger
14 systems, so that bacterial species obtained would be in the thermophillic range to ascertain if
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16 bioelectricity generation rates could be improved upon.
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18 Acknowledgments
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21 The authors would like to thank Dr Denver Cheddie, Head of the Department of Utilities Engineering
22 at the University of Trinidad and Tobago, for providing support and partially funding this research
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24 initiative. The project was also supported by Key North Engineering, St. Augustine, Trinidad, West
25 Indies.
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27
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44 5. Feng, Y., Wang, X., Logan, B.E., and Lee, H.: Brewery wastewater treatment using air-cathode
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