Title Indonesian Journal of Environmental Management and Sustainability e-ISSN:2598-6279 p-ISSN:2598-6260 Research Paper Energy Conversion of Industrial Wastewater on Microbial Fuel Cell (MFC)-Based with Biocatalysts and Pretreatments: A Review Iva Yenis Septiariva1, I Wayan Koko Suryawan2*, Ariyanti Sarwono2 1Sanitary Engineering Laboratory, Study Program of Civil Engineering, Universitas Sebelas Maret, Jalan Ir Sutami 36A, Indonesia 2Department of Environmental Engineering, Faculty of Infrastructure Planning, Universitas Pertamina, Komplek Universitas Pertamina, Jalan Sinabung II, Terusan Simprug, Jakarta 12220, Indonesia *Corresponding author e-mail: i.suryawan@universitaspertamina.ac.id Abstract The purpose of this review is to provide current information regarding industrial wastewater treatment with Microbial Fuel Cell (MFC) technology with the addition of biocatalysts and pretreatments. Moreover, this review also updates on industrial waste treatment technology with MFC technology in Indonesia. Industries produce waste with relatively high organic content. However, this organic material is not easily degraded by biological treatment. Instead of reusing, wastewater treatment, presently, aims merely to meet standards quality. In Indonesia, the reuse processes which generate energy are still rare. Industries that can process and convert wastewater to energy can help the government implement sustainable development in the energy sector. One of the technologies is MFC. MFC uses anode in wastewater as a substrate source and generates electrons under anaerobic conditions. Electron formation could be accelerated by adding biocatalysts such as enzymes and specific microorganisms. The process occurred in an anaerobic anode could be enhanced by increasing the substrate’s biodegradability in waste. The biodegradability can be improved by pretreatment with ozone or ultrasonic technology. In Indonesia, research on industrial wastewater treatment with MFC as well as biocatalyst and pretreatment is limited. Keywords MFC, Waste to Energy, Industrial Wastewater, Electrochemical, Anaerobic, Biocatalyst Received: 25 October 2020, Accepted: 28 November 2020 https://doi.org/10.26554/ijems.2020.4.4.102-109 1. INTRODUCTION Urbanization and industrialization in developing countries like Indonesia create problems in the treatment and disposal of wastewater and energy needs. This situation causes severe problems of public and environmental health, especially in the aspect of sustainable development. The sustainable development goals (SDGs) are access to clean, affordable, and sustainable energy. Stakeholders need to minimize the use of fossil fuel energy and its resulting pollution. The need for fuel energy and depletion of fossil fuels has resulted in the demand for alternative energy in var- ious research fields to find potential, economical, and the manufacture of renewable energy sources.. Renewable en- ergy development is expected to reduce the dependence on fossil fuels and to increase energy independence in each country (Kaygusuz, 2012). Indonesian Government Regu- lation No.79/2014 concerning National Energy Policy is a clear form of the government’s efforts to achieve sustainable development goals in the energy sector. This policy aims to reduce fossil fuel used by less than 25% and to increase renewable energy use by more than 23% (Ramadan, 2017). Renewable energy has provided great benefits, especially for electricity, including increasing economic, social, and public health value. Some areas in Indonesia are not entirely self-sufficient, therefore they are not covered by electricity in rural areas and, even, in urban areas. This concern could accelerate the development of alternative energy sources, such as fuel cells (Sivagami, 2015; Martinez-Duart et al., 2015; Salvi and Subramanian, 2015; Guo et al., 2014). In Indonesia, industries is one of the largest energy users and producers of waste that are not environmentally friendly. The reduction of ecosystems and the health impacts of indus- trial pollutants have necessitated the development of various advanced processing technologies. Processing technology applications are still limited due to high energy requirements and other chemical consumption and complex operations and maintenance. Industrial waste such as agricultural, plantation, palm oil, textiles, pier, and household are ideal substrate for the production of alternative energy because it was rich with organic content. Organic materials in this https://doi.org/10.26554/ijems.2020.4.4.102-109 Septiariva et. al. Indonesian Journal of Environmental Management and Sustainability, 4 (2020) 102-109 wastewater were highly considered in waste to energy tech- nology. The treating process of wastewater with the method of (Feng et al., 2008) Microbial Fuel Cell (MFC) emerged as an alternative in the late 1990s. The history of this technology began in 1912, with Potter as the founder (Potter, 1911) . MFC is a methodology that reuses and reduces energy demand. Recently, the production of valuable energy and other by-products were more critical. MFC is a system in which chemical energy is converted into electrical energy or bio-electrochemical systems (BES) by catalytic reactions of microorganisms (Kondaveeti et al. (2014); Logan et al. (2006)) . Other BES have been developed to produce useful products, such as hydrogen (Santoro et al. (2017);Escapa et al. (2016)), methane (Babanova et al. (2016); Villano et al. (2011);Van Eerten-Jansen et al. (2012)), or desalinated water (Cao et al., 2009). Many things need to be conducted before reaching the industrialization of MFCs (Trapero et al. (2017); Rahimne- jad et al. (2015)). The implementation of industrial waste is more complicated because it has to work in more complex conditions (Pant et al. (2010);Pandey et al. (2016)). Several innovations that can be combined are the addition of bio- catalysts and pretreatments. This innovation can be used as a reference of a starting point for MFC industrialization growth, especially in Indonesia. This review aims to identify the type of MFC use in the wastewater industry and the challenge of using biocatalyst waste and pretreatment in MFC applications. 2. EXPERIMENTAL SECTION 2.1 Methods This study uses a review obtained from the google scholar database. Identification was carried out using the keyword of Microbial Fuel Cell (MFC). The data used were data from journal sources, proceedings, and dissertations. Data were analyzed using descriptive. Previous research results from journals, proceedings, and dissertations were compared. 3. RESULTS AND DISCUSSION 3.1 Previous Research The MFC research that has been conducted currently fo- cuses more on laboratory scale reactors while the application in the field is required to use a relatively large scale. Several laboratory-scale research results on industrial waste have re- sulted in developments that have the potential to be applied in the field. The summary of this study are described in Table 1. Researches on the addition of the catalyst shown in Table 2 are quite potential. Pretreatment also has the potential to increase the value of energy conversion and waste treatment as shown in Table 3. 3.2 Develops Scale of MFC reactor Several groups have examined MFC as a reactor for wastew- ater treatment from the lab scale to pilot scale. Upscaling to a volume of 1 m3 aimed at treating the wastewater of a brewery in Yatala, Queensland, Australia has been carried out with satisfactory results (Logan, 2010). A 105 L MFC unit pilot system was also recently implemented (Zhang and He, 2015). In these examples, the primary objective is to detect compounds or degradation of organic and energy potential. The forecast for cheap electricity prices grow as the use of MFC will be a promising alternative. MFC reactor performance from operating variables such as COD, flow rate, or reactor volume might vary depending on the application and wastewater, and making it a useful tool for future assessment by potential investors in this technology (Trapero et al., 2017). Applications of MFC have been reported to meteoro- logical power buoys (Tender et al., 2008) and wireless tem- perature sensors (Dewan et al. (2014);Ewing et al. (2014)). Other types of MFC have also demonstrated the capabil- ity of turning on environmental sensors (Schievano et al. (2017);Khaled et al. (2016);Pietrelli et al. (2014)). Several other applications have been reported, including charging mobile phones (Ieropoulos et al., 2013) and on smartphones (Walter et al., 2017) as well as LEDs for lightning (Gajda et al., 2015). This particular application has been devel- oped for trials in refugee camps and slums (Ieropoulos et al., 2016). 3.3 Administration of biocatalysts in MFC Currently, MFC research commonly uses artificial wastewa- ter instead of actual wastewater ( Pant et al. (2010);Pandey et al. (2016)). The use of MFC reactors for research was limited to a laboratory scale with a volume of less than 1 L. Large scale MFC reactor has also been conducted, but the reactor with such volume only potentially degrades or- ganic compounds in waste ( Zhang and He (2015);Ge et al. (2015)). In general, waste has low biodegradability but high or- ganic content,particularly for some industries such as textiles and even metals (Apritama et al., 2020). Much industrial wastewater is treated in conventional ways (Suryawan et al., 2019). Some industrial waste, which cannot be treated con- ventionally, utilizes organic material contained in the waste. The conversion of waste energy could be accelerated by adding a biocatalystsuch as microorganisms (bioaugmenta- tion). This review focuses on the addition of the enzyme from agricultural waste into the MFC reactor. Agricultural wastes such as straw, rice husk, and corn could potentially produce specific enzymes that were able to accelerate the substrate degradation rate in waste. The high organic content and low BOD content in industrial waste cause a low biodegradability value and leads to biological processing difficulty. Thus, preliminary processing (pretreatment) are needed to increase the biodegradability of the waste. Some of the MFC reactor integrated pretreatments were carried out such as ozone and ultrasonic (Yusoff et al., 2013) . There was still a © 2020 The Authors. Page 103 of 109 Septiariva et. al. Indonesian Journal of Environmental Management and Sustainability, 4 (2020) 102-109 Table 1. Laboratory scale MFC research on industrial waste No MFC system Types of Industrial Waste Ref 1 Dual-chamber with aeration and Composite industrial wastewater (Mohan et al., 2009) addition of potassium ferricyanide (18.6 g COD/L; 56.8 g TDS/L). catholyte 2 Dual-chamber MFC with the addition H2O2 added in colored wastewater and (Fu et al., 2010) of the Fenton system anode chamber in sequential operation. 3 MFC with dual-chamber with ozone Polymer wastewater with a 165 ml volume (Li et al., 2017) membrane (0.08–0.12 g/L) with a cathode of 1 M HCl and 1 M NaOH. 4 Dual-chamber MFC with a Substrate and anodes from leather, dairy, (Aswin et al., 2017) volume of 500 mL and domestic industrial wastewater. 5 Single chamber with batch The substrate from the oil refinery (Srikanth et al., 2016) and continuous conditions with wastewater is processed continuously. the volume of 0.25/0.20 L 6 Single chamber in batch condition Pharmaceutical wastewater was obtained (Velvizhi and Mohan, 2012) with volume 0.5/0.43 L from the massive drug manufacturing unit. 7 The anaerobic consortium obtained from a Single MFC (nonmediator; Full-scale anaerobic sludge blanket reactor (Goud and Mohan, 2011) non-catalytic graphite (UASB) operating with composite chemical electrode; open-air cathode). wastewater used as a biocatalyst in the MFC anode chamber. 8 Pre-fermentation & UBFC with The waste substrate from biodiesel (Sukkasem, 2013) the addition of a biocatalyst wastewater, palm oil, and seafood. 9 Single Chamber MFC reactor with Petroleum refinery wastewater (Mohanakrishna et al., 2018a)a total and working volume used as a substrate of 350 and 300 mL, respectively. and alkalinity. 10 The 4L anoxic aerobic MFC reactor (Fazli et al., 2018) was used for this study. The MFC Used caustic wastewater is industrial reactor was inoculated with aerobic wastewater with high COD concentration sludge and operated in continuous influenced by high sulfur content, salinity, HRT and SRT mode for 20 days. 11 Both the anode and cathode electrodes (Jiang et al., 2011) Plexiglas dual-chamber MFC pressed consist of graphite fiber brushes and to both sides of the proton exchange titanium wires that collects electrons for membrane (PEM) without tubes. the external circuit.The anodic compartment of MFC is inoculated with activated sludge. 12 POME (Palm Oil Mill Effluent) organic (Yogaswara et al., 2017) The design type of dual-chamber waste in the anode compartment with MFC has two chambers consisting of variations addition of Escherichia coli anode and cathode compartments. and Saccharomyces cerevisiae (10% v/v). Each volume was 500 ml. The cathode compartment contains 200 ppm KMnO4 solution and aerobically conditioned with the aid of an aerator. © 2020 The Authors. Page 104 of 109 Septiariva et. al. Indonesian Journal of Environmental Management and Sustainability, 4 (2020) 102-109 small number of research that focused on MFC substrates pretreatment and needs to be studied further, especially in the field of industrial wastewater. 3.4 MFC integrated waste pre-treatment Ultrasonic waves are longitudinal mechanical waves with frequencies above 20 kHz. These waves could propagate in solid, liquid, and gas mediums due to interaction with molecules and the inertia properties of the medium passed through (Ramadan, 2017). Industrial wastewater usually has a very low biodegrad- ability index thereforeprocessing applications using microor- ganisms is a major challenge. Some pretreatments are impor- tant to increase the biodegradability index (BOD5/COD). The higher biodegradability index is a measure for the biodegradability increase of organic pollutant degradation. This biodegradability increase could be achieved when the COD removal is moderate, and the ozonation time is short. Besides, the pretreatment process was suitable for a biodegrad- ability index of less than 0.3 and increased it to be greater than 0.4. Several studies have also shown the ozonation suc- cess in increasing the industrial wastewater biodegradability (Suryawan et al. (2019); Suryawan et al. (2020)). 3.5 Wastewater treatment industry development with MFC Along with the times, the population in the world, including Indonesia, is increasing. The existence of rapid population growth demands living facilities used to meet various needs. Therefore, more and more industries are being built and op- erating to meet people’s needs in Indonesian and the world. The development of industrial centers could be followed by higher waste generation, one of which is wastewater. This industrial wastewater needs to be treated beforehand to com- ply with quality standards if discharged into a water body. This domestic liquid waste could be processed using the MFC system to reduce organic contaminants by degrading this organic material into electricity. For high concentration of COD, the longer the degradation process, the greater the anode compartment of the proton ions (H+) and electrons (e−) would be (Haslett, 2012). Various utilization of MFC technology in Indonesia still focuses on domestic wastewater and leachate water. Meanwhile, the utilization of industrial wastewater is still low. Table 4 shows various research that utilizes industrial waste for MFC technology. Dual chamber modifiedMFC technology generally dom- inates industrial wastewater conversion to energy. There are few reported literature on MFC using catalysts for in- dustrial wastewater media, thus it is necessary to conduct further research using biocatalysts such as bioaugmentation with microorganisms. The findings will undoubtedly offer economic, social and environmental benefits. 4. CONCLUSIONS MFC technology for wastewater treatment has not been widely developed. Waste could be generated from domestic activities along with non-domestic activities, such as indus- tries. Research in MFC is mostly limited to the laboratory scale. Studies using both biocatalysts and pretreatments can be potentially developed to improve the MFC technology. In Indonesia, MFC work has been carried out in several indus- tries and has produced acceptable results. However, MFC technology development needs to be furtherexplored, using biocatalysts, ozone, and ultrasonic pretreatment to compro- mise the challenges in current treatment technology using microorganisms. The pretreatments can improve biodegrad- ability index (BOD5/COD). Microbial Fuel Cell technology utilizes microorganism toreduce the organic contaminants by degrading this organic substances and converting into electricity. MFC treatment uses anode in wastewater as a substrate source and generates electrons under anaero- bic conditions. Electron formation could be accelerated by adding biocatalysts such as enzymes and specific microor- ganisms. The anodic compartment of MFC technology is inoculated with activated sludge from biological treatment. REFERENCES Ali, M. and A. A. Widodo (2019). Biokonversi Bahan Organik pada Limbah Cair Rumah Pemotongan Hewan menjadi Energi Listrik menggunakan Microbial Fuel Cell. ENVIROTEK: Jurnal Ilmiah Teknik Lingkungan, 11(2); 30–37 Apritama, M. R., I. Suryawan, A. S. Afifah, and I. Y. Sep- tiariva (2020). Phytoremediation of effluent textile wwtp for NH3-N and Cu reduction using pistia stratiotes Aswin, T., S. Begum, and M. Y. Sikkandar (2017). 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Previous MFC research with the addition of biocatalysts No Biocatalysts used The effect of adding biocatalyst Ref 1 The addition of an electrogenic (Srikanth et al., 2016) mixed culture of rusted metal The electrode dominated by iron bacteria, surface area was smaller, sulfur oxidizer producer bacteria, but the power yield was and acid bacteria was used good enough for as the inoculum. process improvement. 2 The anaerobic consortium The electrogenic activity of a taken from the anaerobic fuel cell depends on many pharmaceutical wastewater factors, especially the microorganisms’ scale was used as a biocatalyst in catabolic activity used the anodic chamber in MFC. as anodic biocatalysts. 3 Food waste processing that A significant increase (Goud and Mohan, 2011) has been previously in power output fermented in an anaerobic was seen reactor for 24 hours after fermentation with a consortium of the anaerobic mixture as a biocatalyst, at pH 7 under anaerobic conditions 4 Immobilized biocatalytic basic (Sukkasem, 2013) electrode, each material was The carbon fiber brush inoculated in activated sludge immobilization base obtained from industrial waste was increased UBFC water treatment plants performance by 17.54%. 5 Wastewater is a good source This resulted in an increase of 30% (Mohanakrishna et al., 2018b)of several bacterial strains types in COD removal compared to MFC at the anode and cathode. with biocatalyst at the anode. 6 The contribution of direct Fapetu et al. 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Previous MFC research with pretreatment No Type of Pretreatment Result Ref 1 Ultrasound pretreatment MFC with an electrical load > 0.6 W / ml (Jiang et al., 2011)increased the total COD removal rate from 11.3% to 19.2% 2 Ozone pretreatment Pretreatment was carried out using ozone (Yusoff et al., 2013) and microwave. Ozonation was carried out for 2 and 4 hours. When 2- and 4-hour samples of ozonation were introduced in the MFC reactor, the voltages were increased to more than 150 mV and 120 mV respectively. Ewing, T., J. T. Babauta, E. Atci, N. Tang, J. Orellana, D. Heo, and H. Beyenal (2014). Self-powered wastewater treatment for the enhanced operation of a facultative lagoon. Journal of Power Sources, 269; 284–292 Fapetu, S., T. Keshavarz, M. Clements, and G. Kyazze (2016). Contribution of direct electron transfer mecha- nisms to overall electron transfer in microbial fuel cells utilising Shewanella oneidensis as biocatalyst. Biotechnol- ogy letters, 38(9); 1465–1473 Fazli, N., N. S. 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Previous MFC research with pretreatment No Wastewater type Catalyst Volume MFC type COD Electricity Source removal Generation 1 Pulp and Paper - 3.47 L ML-MFC 38.50% (Pramono et al., 2015)Industry (Membrane less 118.8 mV Microbial Fuel Cell) 2 Fishery industry - 1.8 L Single chamber 59.34% 340 mV (Ibrahim et al., 2017) MFC 3 Pome E.coli 500 ml Dual-chamber 14.23% 103.02 (Yogaswara et al., 2017) mW/m2 4 Tempe and Lactobacillus 1 L Dual-chamber - 282 mV (Sulistiyawati, 2020) Tofu Waste bulgaricus 5 Tempe liquid 0.1N 800 ml Dual-chamber - 675 mV (Syahri et al., 2019)waste electrolyte solution 6 Slaughterhouse - 1 L Dual-chamber 71% 4738.55 (Ali and Widodo, 2019) mW/m2 7 Preserve fish - - Dual-chamber 90% 6.84 mW (Ibrahim et al., 2020)without drying (pindang) waste 8 Fish fillet - 2 L Single chamber 77.92% 550 V (Safitri et al., 2020) industrial waste MFC other bioelectrochemical systems. Applied microbiology and biotechnology, 85(6); 1665–1671 Logan, B. E., B. Hamelers, R. Rozendal, U. 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Bioresource technology, 145; 90–96 Zhang, F. and Z. He (2015). Scaling up microbial desali- nation cell system with a post-aerobic process for simul- taneous wastewater treatment and seawater desalination. Desalination, 360; 28–34 © 2020 The Authors. Page 109 of 109 INTRODUCTION EXPERIMENTAL SECTION Methods RESULTS AND DISCUSSION Previous Research Develops Scale of MFC reactor Administration of biocatalysts in MFC MFC integrated waste pre-treatment Wastewater treatment industry development with MFC CONCLUSIONS