Nitrogen removal in a single-chamber microbial fuel cell with nitrifying biofilm enriched at the air cathode

Nitrogen removal is needed in microbial fuel cells (MFCs) for the treatment of most waste streams. Current designs couple biological denitrification with side-stream or combined nitrification sustained by upstream or direct aeration, which negates some of the energy-saving benefits of MFC technology. To achieve simultaneous nitrification and denitrification, without extra energy input for aeration, the air cathode of a single-chamber MFC was pre-enriched with a nitrifying biofilm. Diethylamine-functionalized polymer (DEA) was used as the Pt catalyst binder on the cathode to improve the differential nitrifying biofilm establishment. With pre-enriched nitrifying biofilm, MFCs with the DEA binder had an ammonia removal efficiency of up to 96.8% and a maximum power density of 900 ± 25 mW/m², compared to 90.7% and 945 ± 42 mW/m² with a Nafion binder. A control with Nafion that lacked nitrifier pre-enrichment removed less ammonia and had lower power production (54.5% initially, 750 mW/m²). The nitrifying biofilm MFCs had lower Coulombic efficiencies (up to 27%) than the control reactor (up to 36%). The maximum total nitrogen removal efficiency reached 93.9% for MFCs with the DEA binder. The DEA binder accelerated nitrifier biofilm enrichment on the cathode, and enhanced system stability. These results demonstrated that with proper cathode pre-enrichment it is possible to simultaneously remove organics and ammonia in a single-chamber MFC without supplemental aeration.     

新型滴滤式生物阴极微生物燃料电池的性能研究

设计了新型滴滤式生物阴极微生物燃料电池(MFC),考察了其产电及污水净化特性。滴滤式MFC阴极的充氧效果良好,稳定产电的电流密度高达39 A/m3,最佳阴极循环流量为120 mL/min,此时最大功率密度为91.2 W/m3。滴滤式MFC可以实现阳极除碳、阴极硝化,对COD和NH4+-N的去除率分别为72.8%和98.7%,且阴极的硝化过程在一定程度上缓解了阴极pH值的升高。滴滤式MFC能够在无机械曝气的条件下维持产电和净化污水效能,其低能耗的特点为MFC的实际应用提供了一种新的解决方案。     

Up-scaling microbial fuel cell systems for the treatment of real textile dye wastewater and bioelectricity recovery

ABSTRACT

In this work the energy recovery in microbial fuel cell was studied by electrically stacking its three individual units into series and parallel arrangements. The power output was higher in parallel stacking by 2.07 and 14.77 times than series and individual units respectively. The rate of degradation of dye wastewater was in order of individual Microbial Fuel Cell (MFC) < series stack < parallel stack. The corn cob biochar was used as an additive in the MFC to improve the efficiency of the individual MFC unit. The addition of 0.5 g corn cob biochar enhanced the power output to 38.6 mW/m² from 0.47 mW/m² in the MFC individual unit without the biochar additive. The simultaneous COD reduction, TDS reduction and decolourisation of dye wastewater achieved are 82.14%, 68% and 74.8% respectively. The current work demonstrates that the dose of biochar and parallel stacking are a framework to achieve enhanced dye removal and bioenergy recovery via microbial fuel cell.     

Non‐steroidal anti‐inflammatory pharmaceutical wastewater treatment using a two‐chambered microbial fuel cell

The two‐chambered microbial fuel cell (MFC) was designed and used for studying the efficiency of the real wastewater treatment from a non‐steroidal anti‐inflammatory pharmaceutical plant as well as from synthetic wastewater containing diclofenac sodium (DS). The removal of the contaminants was expressed regarding chemical oxygen demand (COD) removal, as measured by spectrophotometry experiments. Moreover, the effect of two different types of the cathode on current characteristics and COD removal was investigated. This research showed that the Pt‐coated Ti cathode could lead to higher efficiency of both power density and COD removal. In this case, the results indicated that the maximum power density (P_max) was 20.5 and 6.5 W/m³ and the maximum COD removal was 93 and 78% for MFCs using real and synthetic wastewater, respectively.     

Electricity generation from cysteine in a microbial fuel cell

In a microbial fuel cell (MFC), power can be generated from the oxidation of organic matter by bacteria at the anode, with reduction of oxygen at the cathode. Proton exchange membranes used in MFCs are permeable to oxygen, resulting in the diffusion of oxygen into the anode chamber. This could either lower power generation by obligate anaerobes or result in the loss in electron donor from aerobic respiration by facultative or other aerobic bacteria. In order to maintain anaerobic conditions in conventional anaerobic laboratory cultures, chemical oxygen scavengers such as cysteine are commonly used. It is shown here that cysteine can serve as a substrate for electricity generation by bacteria in a MFC. A two-chamber MFC containing a proton exchange membrane was inoculated with an anaerobic marine sediment. Over a period of a few weeks, electricity generation gradually increased to a maximum power density of 19 mW/m(2) (700 or 1000 Omega resistor; 385 mg/L of cysteine). Power output increased to 39 mW/m(2) when cysteine concentrations were increased up to 770 mg/L (493 Omega resistor). The use of a more active cathode with Pt- or Pt-Ru, increased the maximum power from 19 to 33 mW/m(2) demonstrating that cathode efficiency limited power generation. Power was always immediately generated upon addition of fresh medium, but initial power levels consistently increased by ca. 30% during the first 24 h. Electron recovery as electricity was 14% based on complete cysteine oxidation, with an additional 14% (28% total) potentially lost to oxygen diffusion through the proton exchange membrane. 16S rRNA-based analysis of the biofilm on the anode of the MFC indicated that the predominant organisms were Shewanella spp. closely related to Shewanella affinis (37% of 16S rRNA gene sequences recovered in clone libraries).     

Electricity generation from swine wastewater using microbial fuel cells

Microbial fuel cells (MFCs) represent a new method for treating animal wastewaters and simultaneously producing electricity. Preliminary tests using a two-chambered MFC with an aqueous cathode indicated that electricity could be generated from swine wastewater containing 8320 +/- 190 mg/L of soluble chemical oxygen demand (SCOD) (maximum power density of 45 mW/m2). More extensive tests with a single-chambered air cathode MFC produced a maximum power density with the animal wastewater of 261 mW/m2 (200 omega resistor), which was 79% larger than that previously obtained with the same system using domestic wastewater (146 +/- 8 mW/m2) due to the higher concentration of organic matter in the swine wastewater. Power generation as a function of substrate concentration was modeled according to saturation kinetics, with a maximum power density of P(max) = 225 mW/m2 (fixed 1000 omega resistor) and half-saturation concentration of K(s) = 1512 mg/L (total COD). Ammonia was removed from 198 +/- 1 to 34 +/- 1 mg/L (83% removal). In order to try to increase power output and overall treatment efficiency, diluted (1:10) wastewater was sonicated and autoclaved. This pretreated wastewater generated 16% more power after treatment (110 +/- 4 mW/m2) than before treatment (96 +/- 4 mW/m2). SCOD removal was increased from 88% to 92% by stirring diluted wastewater, although power output slightly decreased. These results demonstrate that animal wastewaters such as this swine wastewater can be used for power generation in MFCs while at the same time achieving wastewater treatment.     

Microbial fuel cells for simultaneous carbon and nitrogen removal

The recent demonstration of cathodic nitrate reduction in a microbial fuel cell (MFC) creates opportunities for a new technology for nitrogen removal from wastewater. A novel process configuration that achieves both carbon and nitrogen removal using MFC is designed and demonstrated. The process involves feeding the ammonium-containing effluent from the carbon-utilising anode to an external biofilm-based aerobic reactor for nitrification, and then feeding the nitrified liquor to the MFC cathode for nitrate reduction. Removal rates up to 2 kg COD m(-3)NCC d(-1) (chemical oxygen demand: COD, net cathodic compartment: NCC) and 0.41 kg NO(3)(-)-Nm(-3)NCC d(-1) were continuously achieved in the anodic and cathodic compartment, respectively, while the MFC was producing a maximum power output of 34.6+/-1.1 Wm(-3)NCC and a maximum current of 133.3+/-1.0 Am(-3)NCC. In comparison to conventional activated sludge systems, this MFC-based process achieves nitrogen removal with a decreased carbon requirement. A COD/N ratio of approximately 4.5 g COD g(-1) N was achieved, compared to the conventionally required ratio of above 7. We have demonstrated that also nitrite can be used as cathodic electron acceptor. Hence, upon creating a loop concept based on nitrite, a further reduction of the COD/N ratio would be possible. The process is also more energy effective not only due to the energy production coupled with denitrification, but also because of the reduced aeration costs due to minimised aerobic consumption of organic carbon.     

Operation of a horizontal subsurface flow constructed wetland – Microbial fuel cell treating wastewater under different organic loading rates

The aim of the present work is to determine whether a horizontal subsurface flow constructed wetland treating wastewater could act simultaneously as a microbial fuel cell (MFC). Specifically, and as the main variable under study, different organic loading rates were used, and the response of the system was monitored. The installation consisted of a synthetic domestic wastewater-feeding system and a pilot-scale constructed wetland for wastewater treatment, which also included coupled devices necessary to function as an MFC. The wetland worked under continuous operation for 180 d, treating three types of synthetic wastewater with increasing organic loading rates: 13.9 g COD m⁻² d⁻¹, 31.1 g COD m⁻² d⁻¹, and 61.1 g COD m⁻² d⁻¹. The COD removal efficiencies and the cell voltage generation were continuously monitored. The wetland worked simultaneously as an MFC generating electric power. Under low organic loading rates, the wastewater organic matter was completely oxidised in the lower anaerobic compartment, and there were slight aerobic conditions in the upper cathodic compartment, thus causing an electrical current. Under high organic loading rates, the organic matter could not be completely oxidised in the anodic compartment and flowed to the cathodic one, which entered into anaerobic conditions and caused the MFC to stop working. The system developed in this work offered similar cell voltage, power density, and current density values compared with the ones obtained in previous studies using photosynthetic MFCs, sediment-type MFCs, and plant-type MFCs. The light/darkness changes caused voltage fluctuations due to the photosynthetic activity of the macrophytes used (Phragmites australis), which affected the conditions in the cathodic compartment.     

Modelling study of an upflow microbial fuel cell catalysed with anaerobic aged sludge

An electrochemical model for an upflow dual-chambered microbial fuel cell (MFC) process is proposed in this study. The model was set up on the basis of the experimental results and the analysis of biochemical and electrochemical processes in the MFC biocatalysed with anaerobic aged sludge and alternatively fuelled with a synthetic acetate-based and actual domestic wastewaters. Simulation of the process shows that the model describes the process reasonably well with correlation coefficients higher than 0.97. The analysis of model simulation illustrates how the current output depends mainly on the substrate concentration as well as other main variables. The relationship between the current output and over-voltage is revealed by the modelling study. For acetate-based wastewaters with initial chemical oxygen demand (COD) concentrations of 350, 700, 1050, and 1400 mg/L, maximum observed power densities were 290, 405, 448, and 525 mW/m² associated with maximum COD removals of 84%, 88%, 83%, and 82%, respectively.     

Aerobic degradation of acid orange 7 in a vertical-flow constructed wetland

Biological, aerobic degradation of an azo dye and of the resultant, recalcitrant, aromatic amines in a constructed wetland (CW) was demonstrated for the first time. A vertical-flow CW, planted with Phragmites sp. was fed with 127 mg l⁻¹ of acid orange 7 (AO7) at hydraulic loads of 28, 40, 53 and 108 l m⁻²day⁻¹. Color removal efficiencies of up to 99% clearly demonstrate cleavage of the azo bond, also confirmed by the similar AO7 removal and SO₄²⁻ release rates revealing that adsorption onto the matrix was constant. The positive redox potential at the outlet demonstrates that aerobic conditions were present. Chemical oxygen demand and total organic carbon removal efficiencies of up to 93% were also indicative of AO7 mineralization. The degradation of sulfanilic acid was confirmed by the presence of NO₃⁻, SO₄²⁻ and secondary metabolites, which suggest at least two degradation pathways leading to a common compound, 3-oxoadipate.     

Nano-structured manganese oxide as a cathodic catalyst for enhanced oxygen reduction in a microbial fuel cell fed with a synthetic wastewater

Microbial fuel cells (MFCs) provide new opportunities for the simultaneous wastewater treatment and electricity generation. Enhanced oxygen reduction capacity of cost-effective metal-based catalysts in an air cathode is essential for the scale-up and commercialization of MFCs in the field of wastewater treatment. We demonstrated that a nano-structured MnO_x material, prepared by an electrochemically deposition method, could be an effective catalyst for oxygen reduction in an MFC to generate electricity with the maximum power density of 772.8 mW/m³ and remove organics when the MFC was fed with an acetate-laden synthetic wastewater. The nano-structured MnO_x with the controllable size and morphology could be readily obtained with the electrochemical deposition method. Both morphology and manganese oxidation state of the nano-scale catalyst were largely dependent on the electrochemical preparation process, and they governed its catalytic activity and the cathodic oxygen reduction performance of the MFC accordingly. Furthermore, cyclic voltammetry (CV) performed on each nano-structured material suggests that the MnO_x nanorods had an electrochemical activity towards oxygen reduction reaction via a four-electron pathway in a neutral pH solution. This work provides useful information on the facile preparation of cost-effective cathodic catalysts in a controllable way for the single-chamber air-cathode MFC for wastewater treatment.     

Laccase-membrane reactors for decolorization of an acid azo dye in aqueous phase: Process optimization

In the present investigation, performance of various laccase-membrane reactor configurations including direct enzyme contact, enzyme impregnated, immobilized enzyme and a reactor system based on laccase immobilization in chitosan membranes for decolorization of azo dye (acid black 10 BX) were examined using laccase enzyme purified from white rot fungi Pleurotus ostreatus 1804. A five-step laccase purification procedure was employed, which improved the enzymatic activity by 8.27 folds. Laccase was confirmed by comparing with the standard marker using SDS-PAGE electrophoresis, which showed molecular weight of 63 kDa. Experimental data showed that laccase has great potential for color removal without addition of external redox mediators. Various process parameters viz. aqueous phase of pH 6.0, enzyme concentration of 1.75 U/ml, dye concentration of 20 mg/L, temperature of 30 °C and reaction time of 120 min were optimized to achieve maximum decolorization efficiencies. Moreover, different laccase-membrane reactor configurations were tested to determine the efficacy of repeated application of laccase on dye decolorization process. Among the different reactor configurations employed, laccase encapsulated in chitosan membrane showed advantages such as short-term contact period and reusability of enzyme for a number of cycles.     

以葡萄糖为底物的微生物燃料电池产电特性研究

以城市污水处理厂的好氧和厌氧污泥作为接种液,通过构建双室微生物燃料电池,考察了以葡萄糖为底物时连续流微生物燃料电池降解有机物及产电的特性.结果表明:以泡沫镍板、石墨板作为阳极时的产电效果较好;在一定温度范围内,提高温度可增大电池的输出电压和开路电压;对阴极室供氧可提高微生物燃料电池的开路电压和输出电压;随着外接电阻值的增大,微生物燃料电池的输出电流变小,符合原电池电极的一般规律.     

Kinetic characteristics of bacterial azo-dye decolorization by Pseudomonas luteola

A Pseudomonas luteola strain expressing azoreductase activity was utilized to remove the color of an azo dye (reactive red 22) from contaminated solutions. The effects of substrate concentrations, medium compositions, and operation parameters (e.g., pH, temperature, dissolved oxygen, etc.) on decolorization of the azo dye by a P. luteola strain were systematically investigated to reveal the key factors that dominate the performance of azo-dye decolorization. The metabolites resulting from bacterial decolorization were analyzed by high-performance liquid chromatography (HPLC) and mass spectrometery (MS). The results show that the dissolved oxygen and glucose concentration retarded decolorization of reactive red 22 by P. luteola. The optimal azo-dye decolorization occurred at 37 degrees C, while more rapid decolorization took place over pH 7-9. Yeast extract and tryptone strongly enhanced the decolorization. The Michaelis-Menten model can satisfactorily describe the dependence of specific decolorization rate on the concentration of substrate (reactive red 22 or yeast extract). Decolorization of the azo dye by intact cells of P. luteola was essentially independent of the growth phase, whereas the azoreductase activity of the cell-free extract decreased in the order of late-stationary phase > early-stationary phase > mid-log phase. This suggests that mass transfer of the azo dye across the cell membrane may be the rate-limiting step. The HPLC and MS analyses suggest that both partial reduction and complete cleavage of the azo bond could contribute to decolorization of reactive red 22 by P. luteola.     

Redistribution of wastewater alkalinity with a microbial fuel cell to support nitrification of reject water

In wastewater treatment plants, the reject water from the sludge treatment processes typically contains high ammonium concentrations, which constitute a significant internal nitrogen load in the plant. Often, a separate nitrification reactor is used to treat the reject water before it is fed back into the plant. The nitrification reaction consumes alkalinity, which has to be replenished by dosing e.g. NaOH or Ca(OH)₂. In this study, we investigated the use of a two-compartment microbial fuel cell (MFC) to redistribute alkalinity from influent wastewater to support nitrification of reject water. In an MFC, alkalinity is consumed in the anode compartment and produced in the cathode compartment. We use this phenomenon and the fact that the influent wastewater flow is many times larger than the reject water flow to transfer alkalinity from the influent wastewater to the reject water. In a laboratory-scale system, ammonium oxidation of synthetic reject water passed through the cathode chamber of an MFC, increased from 73.8 ± 8.9 mgN/L under open-circuit conditions to 160.1 ± 4.8 mgN/L when a current of 1.96 ± 0.37 mA (15.1 mA/L total MFC liquid volume) was flowing through the MFC. These results demonstrated the positive effect of an MFC on ammonium oxidation of alkalinity-limited reject water.     

Bioaugmented membrane bioreactor (MBR) with a GAC-packed zone for high rate textile wastewater treatment

The long-term performance of a bioaugmented membrane bioreactor (MBR) containing a GAC-packed anaerobic zone for treatment of textile wastewater containing structurally different azo dyes was observed. A unique feeding strategy, consistent with the mode of evolution of separate waste streams in textile plants, was adopted to make the best use of the GAC-zone for dye removal. Dye was introduced through the GAC-zone while the rest of the colorless media was simultaneously fed through the aerobic zone. Preliminary experiments confirmed the importance of coupling the GAC-amended anaerobic zone to the aerobic MBR and also evidenced the efficacy of the adopted feeding strategy. Following this, the robustness of the process under gradually increasing dye-loading was tested. The respective average dye concentrations (mg/L) in the sample from GAC-zone and the membrane-permeate under dye-loadings of 0.1 and 1 g/L.d were as follows: GAC-zone (3, 105), permeate (0, 5). TOC concentration in membrane-permeate for the aforementioned loadings were 3 and 54 mg/L, respectively. Stable decoloration along with significant TOC removal during a period of over 7 months under extremely high dye-loadings demonstrated the superiority of the proposed hybrid process.     

Degradation of a textile reactive Azo dye by a combined chemical-biological process: Fenton's reagent-yeast

This work presents the results of our studies on the decolorization of aqueous azo dye Reactive black 5 (RB5) solution combining an advanced oxidation process (Fenton's reagent) followed by an aerobic biological process (mediated by the yeast Candida oleophila). Under our conditions, initial experiments showed that Fenton's process alone, as well as aerobic treatment by C. oleophila alone, exhibited the capacity to significantly decolorize azo dye solutions up to 200 mg/L, within about 1 and 24h, respectively. By contrast, neither Fenton's reagent nor C. oleophila sole treatments showed acceptable decolorizing abilities for higher initial dye concentrations (300 and 500 mg/L). However, it was verified that Fenton's reagent process lowered these higher azo dye concentrations to a value less than 230 mg/L, which is apparently compatible with the yeast action. Therefore, to decolorize higher concentrations of RB5 and to reduce process costs the combination between the two processes was evaluated. The final decolorization obtained with Fenton's reagent process as primary treatment, at 1.0 x 10(-3)mol/L H(2)O(2) and 1.0 x 10(-4)mol/L Fe(2+), and growing yeast cells as a secondary treatment, achieves a color removal of about 91% for an initial RB5 concentration of 500 mg/L.     

Electro-peroxone treatment of Orange II dye wastewater

Degradation of a synthetic azo dye, Orange II, by electro-peroxone (E-peroxone) treatment was investigated. During the E-peroxone process, ozone generator effluent (O₂ and O₃ gas mixture) was continuously sparged into an electrolysis reactor, which was equipped with a carbon-polytetrafluorethylene (carbon-PTFE) cathode to electrochemically convert the sparged O₂ to H₂O₂. The in-situ generated H₂O₂ then reacted with the sparged O₃ to produce •OH, which can oxidize ozone-refractory organic pollutants effectively. Thus, by simply combining conventional ozonation and electrolysis processes, and using a cathode that can effectively convert O₂ to H₂O₂, the E-peroxone process degraded Orange II much more effectively than the two processes individually. Complete decolorization and 95.7% total organic carbon (TOC) mineralization were obtained after 4 and 45 min of the E-peroxone treatment, respectively. In comparison, only 55.6 and 15.3% TOC were mineralized after 90 min of the individual ozonation and electrolysis treatments, respectively. In addition to its high efficiency, the E-peroxone process was effective over a wide range of pH (3–10) and did not produce any secondary pollutants. The E-peroxone process can thus provide an effective and environmentally-friendly alternative for wastewater treatment.     

Development of an expanded-bed GAC reactor for anaerobic treatment of terephthalate-containing wastewater

An expanded-bed granular activated carbon (GAC) anaerobic reactor was developed to treat terephthalate-containing wastewater. Terephthalate inhibits biological anaerobic degradation of terephthalate and methane production when present at a concentration of more than 150 mg/L. In the GAC anaerobic reactor developed here, degradation of terephthalate and other organic compounds occurred smoothly and stably with removal and methane fermentation ratios of more than 90% under a chemical oxygen demand (COD) loading rate of 4 kg COD/(m³ d) and a terephthalate loading rate of 1 kg terephthalate/(m³ d).     

Investigation of the impacts of thermal pretreatment on waste activated sludge and development of a pretreatment model

This study investigated the impacts of high pressure thermal hydrolysis (HPTH) pretreatment on the distribution of chemical oxygen demand (COD) species in waste activated sludge (WAS). In the first phase of the project, WAS from a synthetically-fed biological reactor (BR) was fed to an aerobic digester (AD). In the second phase, WAS from the BR was pretreated by HPTH at 150 °C and 3 bars for 30 min prior to being fed to the AD. A range of physical, biochemical and biological properties were regularly measured in each process stream in both phases. The COD of the BR WAS consisted of storage products (X_STO), active heterotrophs (X_H) and endogenous decay products (X_E). Pretreatment did not increase the extent to which the BR WAS was aerobically digested and hence it was concluded that the unbiodegradable COD fraction, i.e. X_E, was unchanged by pretreatment. However, pretreatment did increase the rate of degradation as it converted 36% of X_H to readily biodegradable COD (S_B) and the remaining X_H to slowly biodegradable COD (X_B). Furthermore, X_STO was fully converted to S_B by pretreatment. Although pretreatment did not change the VSS concentration in the downstream aerobic digester, it did decrease the ISS concentration by 46 ± 11%. This reduced the total mass of solids produced by the digester by 21 ± 8%. A COD-based HPTH pretreatment model was developed and calibrated. When this model was integrated into BioWin 3.1^®, it was able to accurately simulate both the steady state performance of the overall system employed in this study as well as dynamic respirometry results.