This study explored the influence of azo dye concentration, salinity (with and without aeration) and nitrate concentration on bioelectricity generation and treatment performance in the up-flow constructed wetland-microbial fuel cell (UFCW-MFC) system. The decolourisation efficiencies were up to 91% for 500 mg/L of Acid Red 18 (AR18). However, the power density declined with the increment in azo dye concentration. The results suggest that the combination of salinity and aeration at an optimum level improved the power performance. The highest power density achieved was 8.67 mW/m2. The increase of nitrate by 3-fold led to decrease in decolourisation and power density of the system. The findings revealed that the electron acceptors (AR18, nitrate and anode) competed at the anodic region for electrons and the electron transfer pathways would directly influence the treatment and power performance of UFCW-MFC. The planted UFCW-MFC significantly outweighed the plant-free control in power performance.
To enhance dye removal and energy recovery efficiencies in single-pair electrode photocatalytic fuel cell (PFC-AC), dual cathodes PFC (PFC-ACC) and dual photoanodes PFC (PFC-AAC) were established. Results revealed that PFC-AAC yielded the highest decolorization rate (1.44 h-1) due to the promotion of active species such as superoxide radical (•O2-) and hydroxyl radical (•OH) when the number of photoanode was doubled. The results from scavenging test and UV-Vis spectrophotometry disclosed that •OH was the primary active species in dye degradation of PFC. Additionally, PFC-AAC also exhibited the highest power output (17.99 μW) but the experimental power output was much lower than the theoretical power output (28.24 μW) due to the strong competition of electron donors of doubled photoanodes to electron acceptors at the single cathode and its high internal resistance. Besides, it was found that the increments of dye volume and initial dye concentration decreased the decolorization rate but increased the power output due to the higher amount of sacrificial agents presented in PFC. Based on the abovementioned findings and the respective dye intermediate products identified from gas chromatography-mass spectrometry (GC-MS), the possible degradation pathway of RR120 was scrutinized and proposed.
This study aimed to compare the performance of biofiltration, constructed wetland, and constructed wetland microbial fuel cell (CW-MFC). The transformation from a biofiltration unit to a hybrid CW-MFC was demonstrated with the advantages of improvement of wastewater treatment while generating electricity simultaneously. The introduction of plants to the upper region of the bioreactor enhanced the DO level by 0.8 mg/L, ammonium removal by 5 %, and COD removal by 1 %. The integration of electrodes and external circuits stimulated the degradation rate of organic matter in the anodic region (1 % without aeration and 3 % with aeration) and produced 5.13 mW/m3 of maximum power density. Artificial aeration improved the nitrification efficiency by 38 % and further removed the residual COD to an efficiency of 99 %. The maximum power density was also increased by 3.2 times (16.71 mW/m3) with the aid of aeration. In treating higher organic loading wastewater (3M), the maximum power density showed a significant increment to 78.01 mW/m3 (4.6-fold) and the COD removal efficiency was 98 %. The ohmic overpotential dominated the proportion of total loss (67-91 %), which could be ascribed to the low ionic conductivity. The reduction in activation and concentration loss contributed to the lower internal resistance with the additional aeration and higher organic loading. Overall, the transformation from biofiltration to a hybrid CW-MFC system is worthwhile since the systems quite resemble while CW-MFC could improve the wastewater treatment as well as recover energy from the treated wastewater.
This study demonstrated the effectiveness of single chamber up-flow membrane-less microbial fuel cell (UFML-MFC) in wastewater treatment concurrently with bioelectricity generation. The objectives of this study were to examine the effect of influent substrate concentration (0.405 g/L, 0.810 g/L, 1.215 g/L, 1.620 g/L), anode distributions (11 cm, 17 cm, 23 cm ) and surface morphologies for biofilm formation on the performance of wastewater treatment and power generation. The optimum performance was obtained with substrate concentration of 0.810 g/L. The COD removal efficiency, output voltage, internal resistance, power density and current density obtained were 84.64%, 610 mV, 200 Ω, 162.59 mW/m2 and 468.74 mA/m2, respectively. The Coulombic Efficiency (CE), Normalized Energy Recovery (NERS and NERv) were 1.03%, 789.38 kWh/kg COD and 22.56 kWh/m3, respectively. The results also indicate that the output voltage and power generation obtained in a continuous up-flow MFC were higher with A3 (23 cm), which is of larger electrodes spacing followed by A2 (17 cm) and A1 (11 cm) caused by the enrichment of anaerobic microbial population at A1.
This study demonstrated a successful operation of up-flow constructed wetland-microbial fuel cell (UFCW-MFC) in wastewater treatment and energy recovery. The goals of this study were to investigate the effect of circuit connection, organic loading rates, and electrode spacing on the performance of wastewater treatment and bioelectricity generation. The average influent of COD, NO3(-) and NH4(+) were 624 mg/L, 142 mg/L, 40 mg/L, respectively and their removal efficiencies (1 day HRT) were 99%, 46%, and 96%, respectively. NO3(-) removal was relatively higher in the closed circuit system due to lower dissolved oxygen in the system. Despite larger electrode spacing, the voltage outputs from Anode 2 (A2) (30 cm) and Anode 3 (A3) (45 cm) were higher than from Anode 1 (A1) (15 cm) as a result of insufficient fuel supply to A1. The maximum power density and Coulombic efficiency were obtained at A2, which were 93 mW/m(3) and 1.42%, respectively.
This study demonstrated the potential of single chamber up-flow membrane-less microbial fuel cell (UFML-MFC) in wastewater treatment and power generation. The purpose of this study was to evaluate and enhance the performance under different operational conditions which affect the chemical oxygen demand (COD) reduction and power generation, including the increase of KCl concentration (MFC1) and COD concentration (MFC2). The results showed that the increase of KCl concentration is an important factor in up-flow membrane-less MFC to enhance the ease of electron transfer from anode to cathode. The increase of COD concentration in MFC2 could led to the drop of voltage output due to the prompt of biofilm growth in MFC2 cathode which could increase the internal resistance. It also showed that the COD concentration is a vital issue in up-flow membrane-less MFC. Despite the COD reduction was up to 96%, the power output remained constrained.
The objective of this study was to examine the effects of adsorbability and number of sulfonate group on solar photocatalytic degradation of mono azo methyl orange (MO) and diazo Reactive Green 19 (RG19) in single and binary dye solutions. The adsorption capacity of MO and RG19 onto the TiO₂ was 16.9 and 26.8 mg/g, respectively, in single dye solution, and reduced to 5.0 and 23.1 mg/g, respectively, in the binary dye solution. The data obtained for photocatalytic degradation of MO and RG19 in single and binary dye solution were well fitted with the Langmuir-Hinshelwood kinetic model. The pseudo-first-order rate constants of diazo RG19 were significant higher than the mono azo MO either in single or binary dye solutions. The higher number of sulfonate group in RG19 contributed to better adsorption capacity onto the surface of TiO₂ than MO indicating greater photocatalytic degradation rate.
The application of simultaneous adsorption and biodegradation processes in the same reactor is known to be effective in the removal of both biodegradable and non-biodegradable contaminants in various kinds of wastewater. The objective of this study is to evaluate the efficacy of the two processes under sequencing batch reactor (SBR) operation in treating copper and cadmium-containing synthetic wastewater with powdered activated carbon (PAC) as the adsorbent. The SBR systems were operated with FILL, REACT, SETTLE, DRAW and IDLE periods in the ratio of 0.5: 3.5: 1.0: 0.75 :0.25 for a cycle time of 6 h. In the presence of 10 mg/L Cu(II) and 30 mg/L Cd(II), respectively, the average COD removal efficiencies were above 85% with the PAC dosage in the influent solution at 143 mg/L compared to around 60% without PAC addition. Copper(II) was found to exert a more pronounced inhibitory effect on the bioactivity of the microorganisms compared to Cd(II). It was observed that the combined presence of Cu(II) and Cd(II) did not exert synergistic effects on the microorganisms. Kinetic study conducted for the REACT period showed that the addition of PAC had minimized the inhibitory effect of the heavy metals on the bioactivity of microorganisms.
This study investigates the role of plant (Elodea nuttallii) and effect of supplementary aeration on wastewater treatment and bioelectricity generation in an up-flow constructed wetland-microbial fuel cell (UFCW-MFC). Aeration rates were varied from 1900 to 0mL/min and a control reactor was operated without supplementary aeration. 600mL/min was the optimum aeration flow rate to achieve highest energy recovery as the oxygen was sufficient to use as terminal electron acceptor for electrical current generation. The maximum voltage output, power density, normalized energy recovery and Coulombic efficiency were 545.77±25mV, 184.75±7.50mW/m3, 204.49W/kg COD, 1.29W/m3 and 10.28%, respectively. The variation of aeration flow rates influenced the NO3- and NH4+ removal differently as nitrification and denitrification involved conflicting requirement. In terms of wastewater treatment performance, at 60mL/min aeration rate, UFCW-MFC achieved 50 and 81% of NO3- and NH4+ removal, respectively. E. nuttallii enhanced nitrification by 17% and significantly contributed to bioelectricity generation.
In this study, a membraneless photocatalytic fuel cell with zinc oxide loaded carbon photoanode and platinum loaded carbon cathode was constructed to investigate the impact of dissolved oxygen on the mechanism of dye degradation and electricity generation of photocatalytic fuel cell. The photocatalytic fuel cell with high and low aeration rate, no aeration and nitrogen purged were investigated, respectively. The degradation rate of diazo dye Reactive Green 19 and the electricity generation was enhanced in photocatalytic fuel cell with higher dissolved oxygen concentration. However, the photocatalytic fuel cell was still able to perform 37% of decolorization in a slow rate (k = 0.033 h-1) under extremely low dissolved oxygen concentration (approximately 0.2 mg L-1) when nitrogen gas was introduced into the fuel cell throughout the 8 h. However, the change of the UV-Vis spectrum indicates that the intermediates of the dye could not be mineralized under insufficient dissolved oxygen level. In the aspect of electricity generation, the maximum short circuit current (0.0041 mA cm-2) and power density (0.00028 mW cm-2) of the air purged photocatalytic fuel cell was obviously higher than that with nitrogen purging (0.0015 mA cm-2and 0.00008 mW cm-2).
In this study, the degradation efficiency and electricity generation of the azo dyes affected by the functional groups and molecular structure in a solar photocatalytic fuel cell (PFC) system were investigated and discussed in detail. Four different azo dyes such as, Acid Orange 7 (AO7), Acid Red 18 (AR18), Reactive Black 5 (RB5), Reactive Red 120 (RR120) with different molecular structure were evaluated. The degradation efficiency of AO7, AR18, RB5 and RR120 achieved 5.6 ± 0.3%, 11.1 ± 0.6%, 41.9 ± 0.9% and 52.1 ± 1.3%, respectively, after 6 h irradiated under solar light. In addition, the maximum power density, Pmax for AO7, AR18, RB5 and RR120 was 0.0269 ± 0.01, 0.111 ± 0.03, 1.665 ± 0.67 and 4.806 ± 1.79 mW cm-2, respectively. Meanwhile, the concentration of COD for AO7, AR18, RB5 and RR120 reduced to 16 ± 0.1, 10 ± 0.3, 7 ± 0.6 and 3 ± 0.9 mg L-1, respectively. The concentration ratio of benzene / naphthalene, benzene / azo bond and naphthalene / azo bond, respectively, was analyzed to investigate the impact of the functional groups over photodegradation of the azo dyes in PFC. Electron releasing groups (-OH and -NH2) and electron withdrawing groups (-SO3Na) which attached to the naphthalene or benzene ring also played a pivotal role in the degradation mechanism.
The role of azo dye Reactive Black 5 (RB5) as an electron donor and/or electron acceptor could be distinguished in dual chamber of photocatalytic fuel cell (PFC). The introduction of RB5 in anode chamber increased the voltage generation in the system since degradation of RB5 might produce electrons which also would transfer through external circuit to the cathode chamber. The removal efficiency of RB5 with open and closed circuit was 8.5% and 13.6%, respectively and removal efficiency for open circuit was low due to the fact that recombination of electron-hole pairs might happen in anode chamber since without connection to the cathode, electron cannot be transferred. The degradation of RB5 in cathode chamber with absence of oxygen showed that electrons from anode chamber was accepted by dye molecules to break its azo bond. The presence of oxygen in cathode chamber would improve the oxygen reduction rate which occurred at Platinum-loaded carbon (Pt/C) cathode electrode. The Voc, Jsc and Pmax for different condition of ultrapure water at cathode chamber also affected their fill factor. The transportation of protons to cathode chamber through Nafion membrane could decrease the pH of ultrapure water in cathode chamber and undergo hydrogen evolution reaction in the absence of oxygen which then increased degradation rate of RB5 as well as its electricity generation.
Abstract: Photocatalytic degradation performance is highly related to optimized operating parameters such as initial concentration, pH value, and catalyst dosage. In this study, the impact of various parameters on the photocatalytic degradation of anaerobically digested vinasse (AnVE) has been determined through decolourization and chemical oxygen demand (COD) reduction efficiency using zinc oxide (ZnO) photocatalyst. In this context, the application of photocatalytic degradation in treating sugarcane vinasse using ZnO is yet to be explored. The COD reduction efficiency and decolourization achieved 83.40% and 99.29%, respectively, under the conditions of 250 mg/L initial COD concentration, pH 10, and 2.0 g/L catalyst dosage. The phytotoxicity assessment was also conducted to determine the toxicity of AnVE before and after treatment using mung bean (Vigna radiata). The reduction of root length and the weight of mung bean indicated that the sugarcane vinasse contains enormous amounts of organic substances that affect the plant's growth. The toxicity reduction in the AnVE solution can be proved by UV-Vis absorption spectra. Furthermore, the catalyst recovery achieved 93% in the reusability test. However, the COD reduction efficiency and decolourization were reduced every cycle. It was due to the depletion of the active sites in the catalyst with the adsorption of organic molecules. Thus, it can be concluded that the photocatalytic degradation in the treatment of AnVE was effective in organic degradation, decolorization, toxicity reduction and can be reused after the recovery process.
Hybrid growth microorganisms in sequencing batch reactors have proven effective for treating the toxic compound phenol, but the toxicity effect under different toxicity conditions has rarely been discussed. Therefore, the performance of the HG-SBR under toxic, acute and chronic organic loading can provide the overall operating conditions of the system. Toxic organic loading (TOL) was monitored during the first 7hr while introducing 50mg/L phenol to the system. The system was adversely affected with the sudden introduction of phenol to the virgin activated sludge, which caused a low degradation rate and high dissolved oxygen consumption during TOL. Acute organic loading (AOL) had significant effects at high phenol concentrations (600, 800 1000mg/L). The specific oxygen uptake rate (SOUR) gradually decreased to 4.9mg O2/(g MLVSS·hr) at 1000mg/L of phenol compared to 12.74mg O2/(g MLVSS·hr) for 200mg/L of phenol. The HG-SBR was further monitored during chronic organic loading (COL) over 67days. The effects of organic loading were more apparent at 800mg/L and 1000mg/L phenol concentrations, as the removal range was between 22%-30% and 18%-46% respectively, which indicated the severe effects of COL.
The photocatalytic fuel cell (PFC) system was developed in order to study the effect of several operating parameters in degradation of Reactive Black 5 (RB5) and its electricity generation. Light irradiation, initial dye concentration, aeration, pH and cathode electrode are the operating parameters that might give contribution in the efficiency of PFC system. The degradation of RB5 depends on the presence of light irradiation and solar light gives better performance to degrade the azo dye. The azo dye with low initial concentration decolorizes faster compared to higher initial concentration and presence of aeration in PFC system would enhance its performance. Reactive Black 5 rapidly decreased at higher pH due to the higher amount of OH generated at higher pH and Pt-loaded carbon (Pt/C) was more suitable to be used as cathode in PFC system compared to Cu foil and Fe foil. The rapid decolorization of RB5 would increase their voltage output and in addition, it would also increase their Voc, Jsc and Pmax. The breakage of azo bond and aromatic rings was confirmed through UV-Vis spectrum and COD analysis.
Monoazo and diazo dyes [New coccine (NC), Acid orange 7 (AO7), Reactive red 120 (RR120) and Reactive green 19 (RG19)] were employed as electron acceptors in the abiotic cathode of microbial fuel cell. The electrons and protons generated from microbial organic oxidation at the anode which were utilized for electrochemical azo dye reduction at the cathodic chamber was successfully demonstrated. When NC was employed as the electron acceptor, the chemical oxygen demand (COD) removal and dye decolourisation efficiencies obtained at the anodic and cathodic chamber were 73±3% and 95.1±1.1%, respectively. This study demonstrated that the decolourisation rates of monoazo dyes were ∼50% higher than diazo dyes. The maximum power density in relation to NC decolourisation was 20.64mW/m2, corresponding to current density of 120.24mA/m2. The decolourisation rate and power output of different azo dyes were in the order of NC>AO7>RR120>RG19. The findings revealed that the structure of dye influenced the decolourisation and power performance of MFC. Azo dye with electron-withdrawing group at para substituent to azo bond would draw electrons from azo bond; hence the azo dye became more electrophilic and more favourable for dye reduction.
The main aim of this study is to investigate the performance of organic oxidation and denitrification of the system under long-term operation. The MFC reactor was operated in continuous mode for 180 days. Nitrate was successfully demonstrated as terminal electron acceptor, where nitrate was reduced at the cathode using electron provided by acetate oxidation at the anode. The removal efficiencies of chemical oxygen demand (COD) and nitrate were higher in the closed circuit system than in open circuit system. Both COD and nitrate reduction improved with the increase of organic loading and subsequently contributed to higher power output. The maximum nitrate removal efficiency was 88 ± 4 % (influent of 141 ± 14 mg/L). The internal resistant was 50 Ω, which was found to be low for a double chambered MFC. The maximum power density was 669 mW/m(3) with current density of 3487 mA/m(3).
The under-treated wastewater, especially remaining carcinogenic aromatic compounds in wastewater discharge has been expansively reported, wherein the efficiency of conventional wastewater treatment is identified as the primary contributor source. Herein, the advancement of wastewater treatments has drawn much attention in recent years. In the current study, combined sequential and hybridized treatment of thermolysis and coagulation-flocculation provides a novel advancement for environmental emerging pollutant (EP) prescription. This research is mainly demonstrating the mitigation efficiency and degradation pathway of pararosaniline (PRA) hybridized and combined sequential wastewater treatment. Notably, PRA degradation dominantly via a linkage of reaction: thermal cleavage, deamination, silication and diazene reduction. Thermolysis acts as an initiator for the PRA decomposition through thermally induced bond dissociation energy (BDE) for molecular fragmentation whilst coagulation-flocculation facilitates the formation of organo-bridged silsesquioxane as the final degradation product. Different from conventional treatment, the hybridized treatment showed excellent synergistic degradability by removing 99% PRA and its EPs, followed by combined sequential treatment method with 86% reduction. Comprehensive degradation pathway breakdown of carcinogenic and hardly degradable aromatic compounds provides a new insight for wastewater treatment whereby aniline and benzene are entirely undetectable in effluent. The degradation intermediates, reaction derivatives and end products were affirmed by gas chromatography-mass spectrometry, Fourier transform infrared spectroscopy and ultraviolet-visible spectrophotometry (GC-MS, FTIR and UV-Vis). This finding provides valuable guidance in establishing efficient integrated multiple-step wastewater treatments.
The treatment of single and binary azo dyes, as well as the effect of the circuit connection, aeration, and plant on the performance of UFCW-MFC, were explored in this study. The decolorization efficiency of Remazol Yellow FG (RY) (single dye: 98.2 %; binary dye: 92.3 %) was higher than Reactive Black 5 (RB5) (single: 92.3 %; binary: 86.7 %), which could be due to monoazo dye (RY) requiring fewer electrons to break the azo bond compared to the diazo dye (RB5). In contrast, the higher decolorization rate of RB5 in binary dye indicated the removal rate was affected by the electron-withdrawing groups in the dye structure. The closed circuit enhanced about 2% of color and 4% of COD removal. Aeration improved the COD removal by 6%, which could be contributed by the mineralization of intermediates. The toxicity of azo dyes was reduced by 11-26% and the degradation pathways were proposed. The dye removal by the plants was increased with a higher contact time. RB5 was more favorable to be uptook by the plant as RB5 holds a higher partial positive charge. 127.39 (RY), 125.82 (RB5), and 58.66 mW/m3 (binary) of maximum power density were generated. The lower power production in treating the binary dye could be due to more electrons being utilized for the degradation of higher dye concentration. Overall, the UFCW-MFC operated in a closed circuit, aerated, and planted conditions achieved the optimum performance in treating binary azo dyes containing wastewater (dye: 87-92%; COD: 91%) compared to the other conditions (dye: 83-92%; COD: 78-87%).
This study investigated the effect of different supporting electrolyte (Na2SO4, MgSO4, NaCl) in degradation of Reactive Black 5 (RB5) and generation of electricity. Zinc oxide (ZnO) was immobilized onto carbon felt acted as photoanode, while Pt-coated carbon paper as photocathode was placed in a single chamber photocatalytic fuel cell, which then irradiated by UV lamp for 24 h. The degradation and mineralization of RB5 with 0.1 M NaCl rapidly decreased after 24-h irradiation time, followed by MgSO4, Na2SO4 and without electrolyte. The voltage outputs for Na2SO4, MgSO4 and NaCl were 908, 628 and 523 mV, respectively, after 24-h irradiation time; meanwhile, their short-circuit current density, J SC, was 1.3, 1.2 and 1.05 mA cm(-2), respectively. The power densities for Na2SO4, MgSO4 and NaCl were 0.335, 0.256 and 0.245 mW cm(-2), respectively. On the other hand, for without supporting electrolyte, the voltage output and short-circuit current density was 271.6 mV and 0.055 mA cm(-2), respectively. The supporting electrolyte NaCl showed greater performance in degradation of RB5 and generation of electricity due to the formation of superoxide radical anions which enhance the degradation of dye. The mineralization of RB5 with different supporting electrolyte was measured through spectrum analysis and reduction in COD concentration.