Application of Modified Carbon Anodes in Microbial Fuel Cells

The effect of different carbon anodes was examined in a new design of single chambered microbial fuel cell (SCMFC). The new cell design used a low-cost hydrophilic membrane to replace costly proton exchange membranes and carbon felt and a range of carbon and modified carbon anodes were investigated. The fuel for the SCMFC was brewery wastewater which was diluted with domestic wastewater and the presented microflora acts as a source of electro-active bacteria. The membrane acts as a separator between the anode chamber and an air cathode and allows the transfer of ions based on the wastewater's natural conductivity. The air cathode was carbon black (Ketjen Black EC 300J) which was deposited (1 mg cm⁻² concentration) directly onto the surface of the separator (one side of the membrane). Steady state polarization demonstrated maximum power densities of up to 30 mW m⁻² and a steady state power density of 20 mW cm⁻² at a current density of 110 mA m⁻² was achieved. The best performing anodes were made from carbon modified with quinone/quinoid groups. With unmodified graphite felt (the control anode material) as anode, the maximal power density obtained was 9.5 mW m⁻².     

Removal mechanism of trace oxytetracycline by aerobic sludge

To investigate the mechanism of removal of selected pharmaceuticals in activated sludge systems, laboratory-scale batch experiments were conducted to assess the adsorption and degradation behavior of trace oxytetracycline (OTC). The adsorption equilibrium of OTC was observed in 30 min and the adsorption process could be well described by a pseudo-second-order model with a rate of 0.362 L μg^?1 min^?1. The OTC adsorption rate decreased with increasing temperature and could be fitted by the Freundlich isotherm. The linear partition coefficients (K_d) were 1.19, 0.999, and 0.841 L g^?1 at temperatures of 15, 20, and 25 °C, respectively. Thermodynamic analysis revealed that the adsorption of OTC onto the inactivated sludge was spontaneous (ΔG = ?16.7 to ?17.0 kJ mol^?1), enthalpy-driven (ΔH = ?24.9 kJ mol^?1), entropy-retarded (ΔS = ?27.4 J (mol K)^?1), and predominantly a physical adsorption.     

Ion exchange membrane-assisted electro-activation of aqueous solutions: Effect of the operating parameters on solutions properties and system electric resistance

The properties of electro-activated (EA) aqueous solutions as well as the dynamics of their changes were considered in the current study using aqueous solutions of NaCl and NaHCO₃. The concentrations of the salt solutions were 0.5, 0.25, 0.125 and 0.05 M. The tests were performed at the DC current densities of 25, 37.5, and 50 Å/m². The electro-activation reactor consisted of three individual cells assembled together and separated by anion-exchange (AEM) and cation-exchange (CEM) membranes. During the experiments, four configurations of the membrane placements and solutions concentrations were studied. The obtained results showed the dynamics of the electro-activation process that allows obtaining electro-activated solutions with targeted properties such as pH and oxydo-reduction potential (ORP). It was possible to obtain electro-activated solutions at the anodic side (acid anolyte) with pH of 3.0, 3.5, and 4.0 and ORP of +1100 ± 15 mV when NaCl solution was used as electrolyte. Furthermore, several types of electro-activated solutions with high redox potential (ORP = +921 ± 12 mV) and neutral pH (6.48 ± 0.05) were obtained on the anode side when sodium carbonate was used. At the same time, two types of solutions, one with acid pH (2.14 ± 0.14) and the other one with alkaline pH (10.46 ± 0.03) with ORP = +689 ± 10 and 110 ± 21 mV, respectively, were obtained in the central compartment which considered as electro-activated solutions obtained by means of noncontact electro-activation.     

Removal of toluene vapour from air stream using a biofilter packed with polyurethane foam

Biodegradation of toluene vapour was investigated for 168 days in a polyurethane packed biofilter inoculated with a mixed microbial population. Biofilter consisted of five square cross-section modular units each of size 0.16 m × 0.16 m × 0.20 m and filled with the polyurethane foam cubes up to a height of 0.15 m. Inlet concentration of toluene was varied from 0.04 to 2.5 g m^?3 and the volumetric flow rate of toluene loaded air from 0.06 to 0.90 m³ h^?1.Depending upon initial loading rates, removal efficiency ranging from 68.2 to 99.9% and elimination capacity ranging from 10.85 to 90.48 g h^?1 m^?3 were observed during steady state operations. More than 90% removal efficiency was observed up to an inlet loading rate of 76.3 g h^?1 m^?3. High carbon recovery (>90%) indicated effective biodegradation in the bed. Low variation of pH (7.2–8.8) and pressure drop (45.8–76.3 Pa) was observed. The stability of the biomass was evident from the fast response of the biofilter to shutdown and restartup.     

Decolorization of synthetic Methyl Orange wastewater by electrocoagulation with periodic reversal of electrodes and optimization by RSM

Treatment of Methyl Orange (MO), an azo dye, synthetic wastewater by electrocoagulation with periodic reversal of the electrodes (PREC) was examined. Response Surface Methodology (RSM) was used to optimize the influence of experimental conditions for color removal (CR), energy consumption (ENC), electrode consumption (ELC) and sludge production (SP) per kg MO removed (kg(MO_r)) with optimal conditions being found to be pH 7.4, solution conductivity (к) 9.4 mS cm⁻¹, cell voltage (U) 4.4 V, current density (j) 185 mA cm⁻², electrocoagulation time (T) 14 min, cycle of periodic reversal of electrodes (t) 15 s, inter-electrode distance (d) 3.5 cm and initial MO concentration of 125 mg L⁻¹. Under these conditions, 97 ± 2% color was removed and ENC, ELC and SP were 44 ± 3 kWh kg(MO_r)⁻¹, 4.1 ± 0.2 kg(Al) kg(MO_r)⁻¹ and 17.2 ± 0.9 kg(sludge) kg(MO_r)⁻¹, respectively. With the enhanced electrochemical efficiency resulting from the periodic electrode reversal, the coefficients of increased resistance and decreased current density between the two electrodes in the PREC setup were 2.48 × 10⁻⁴ Ω cm⁻² min⁻¹ and 0.29 mA cm⁻² min⁻¹, respectively, as compared to 7.72 × 10⁻⁴ Ω cm⁻² min⁻¹ and 0.79 mA cm⁻² min⁻¹ as measured for the traditional electrocoagulation process. The rate constant of decolorization was also enhanced by 20.4% from 0.152 min⁻¹ in the traditional electrocoagulation process to 0.183 min⁻¹ in the PREC process. These performance characteristics indicate that the PREC approach may be more promising in terms of practical application, as a cost-effective treatment, than conventional electrocoagulation for textile dye removals.     

Kinetics of nitrate reductive denitrification by nanoscale zero-valent iron

Nanoscale zero-valent iron (Fe⁰) was synthesized for nitrate denitrification. The reduction efficiency of nitrate decreased quickly with increasing initial pH value, increased considerably with the increasing dosage of nanoscale Fe⁰, and did not vary much with initial nitrate concentrations changing from 20 to 50 mg l^?1 when the excessive amount of nanoscale Fe⁰ was utilized. With reductive denitrification of nitrate by nanoscale Fe⁰, the removal rate of nitrate reached 96.4% in 30 min with nanoscale Fe⁰ dosage of 1.0 g l^?1 and pH_in 6.7, and more than 85% of the nitrate was transformed into ammonia. Kinetics analysis in batch studies demonstrates that the denitrification of nitrate by nanoscale Fe⁰ involves reaction on the metal surface, which fits well the pseudo-first order reaction with respect to nitrate concentration. The observed reaction rate constant of reductive denitrification of nitrate was determined to be 0.086 min^?1 with a nanoscale Fe⁰ dosage of 1.0 g l^?1 and pH_in 6.7. Fast and highly effective denitrification can be achieved by nanoscale Fe⁰ compared with commercial Fe⁰ powder, this is due to the extremely high surface area and high reactivity for nanoscale Fe⁰, which can enhance the denitrification efficiencies remarkably.     

Pretreatment of municipal landfill leachate by a combined process

Biodegradability enhancement of landfill leachate using air stripping followed by coagulation/ultrafiltration (UF) processes was introduced. The air stripping process obtained a removal efficiency of 88.6% for ammonia nitrogen (NH₄–N) at air-to-liquid ratio of 3500 (pH 11) for stripping 18 h. The single coagulation process increased BOD/COD ratio by 0.089 with the FeCl₃ dosage of 570 mg l^?1 at pH 7.0, and the single UF process increased the BOD/COD ratio to 0.311 from 0.049. However, the combined process of coagulation/UF increased the BOD/COD ratio from 0.049 to 0.43, and the final biological oxygen demand (BOD), chemical oxygen demand (COD), NH₄–N and colour of leachate were 1223.6 mg l^?1, 2845.5 mg l^?1, 145.1 mg l^?1 and 2056.8, respectively, when 3 kDa molecular weight cut-off (MWCO) membrane was used at the operating pressure 0.7 MPa. In ultrafiltration process, the average solution flux (J_V), concentration multiple (M_C) and retention rate (R) for COD was 107.3 l m^?2 h^?1, 6.3% and 84.2%, respectively.     

Optimization of mixture ratio of electrolyte for reducing activation resistance of proton exchange membrane fuel cell

The purpose of this study is to find an optimal mixture ratio of the platinum-loaded carbon catalyst and the electrolyte in a membrane electrode assembly (MEA) of a proton exchange membrane fuel cell for reducing the activation resistance, which influences the electrochemical surface area, activation polarization, and maximum power density of the MEA. First, mixture ratios of 10, 20, 40, and 60 wt% platinum-loaded carbon catalysts and electrolyte were examined. The results indicated that the fuel cell performance improved for mixing weight ratios of 1.0:2.0 in 10 wt% Pt/C, 1.0:1.8 in 20 wt% Pt/C, 1.0:1.1 in 40 wt% Pt/C, and 1.0:0.5 in 60 wt% Pt/C. Next, we evaluated the activation resistances of the MEA from the AC impedance characteristics using the optimal mixing weight ratio of the platinum-loaded carbon catalyst and the electrolyte. It was found that the activation resistances of the anode and cathode decrease with an increase in the weight ratio of platinum-loaded carbon in the catalyst layer.     

Partial nitritation of landfill leachate with varying influent composition under intermittent aeration conditions

The start-up and operation of a partial nitritation sequencing batch reactor for the treatment of landfill leachate were carried out on intermittent aeration mode. Partial nitrite accumulation was established in 15 days after the mode was changed from continuous aeration to intermittent aeration. Despite the varying influent composition, partial nitritation could be maintained by adjusting the hydraulic retention time (HRT) and the air flow rate. An increase in the air flow rate together with a decrease in air off duration can improve the partial nitritation capacity and eventually result in the development of granular sludge with fine diameters. A nitrogen loading rate of 0.71 ± 0.14 kg/m³/d and a COD removal rate of 2.21 ± 0.13 kg/m³/d were achieved under the conditions of an air flow rate of 19.36 ± 1.71 m³ air/m³/h and an air on/off duration of 1.5 min/0.7 min. When the ratio of total air flux (TAF) to the influent loading rate (ILR) was controlled at the range of 163–256 m³ air/kg COD, a stable effluent NO₃^?–N/NO_x^?–N (NO₂^?–N plus NO₃^?–N) ratio below 13% was achieved. Interestingly, the effluent pH was found to be a good indicator of the effluent NO₂^?–N/NH₄⁺–N ratio, which is an essential parameter for a subsequent anaerobic ammonium oxidation (Anammox) reactor.     

Biofiltration of gas-phase hexane and toluene mixture under intermittent loading conditions

This paper reports the performance of a compost biofilter subjected to periodic intermittent loads of gas-phase hexane and toluene. The biofilter was operated for 10 h per day, at different empty bed residence times (4, 2 and 1.3 min), and at different inlet concentrations of hexane and toluene, varying between 2 and 3.8 g m^?3, respectively. Steady-state removal efficiency profiles, reaching more than 90% for both the pollutants, was observed after 44 days of operation. Periodic operation of the compost biofilter was characterized by an adsorption step, followed by biological conversion of the pollutants by the microorganisms inherent to the compost. After resuming daily biofilter operation, the required times for biochemical reaction to dominate the initial adsorption step was observed to be 2.5 and 1 h, respectively, for toluene and hexane. The maximum elimination capacity due to the biological step was found to be 61.6 g m^?3 h^?1. The results from this study showed the effectiveness of the biofilter to handle mixtures of gas-phase pollutants, subjected to regular intermittent operations, thus proving their worthiness for industrial use.     

Comparative response of two organic biofilters treating ethylbenzene and toluene after prolonged exposure

The response of two biofilters filled with an organic waste material for treating ethylbenzene and toluene was studied for 415 and 472 operating days, respectively. The peak elimination capacities (EC_MAX) recorded were 170 g m^?3 h^?1 for ethylbenzene (EC_MAX) and 138 g m^?3 h^?1 for toluene. Regarding the degradation profile through the biofilters, an increase in the inlet concentration displaced the degradation profile into the downstream section. A sudden decrease in the performance of both biofilters occurred when the moisture content (MC) of the packing material exceeded 37% for ethylbenzene and 30% for toluene. Thus, a recommended MC value was established in the 15–30% range. Given the bioreactor was operated at a low MC level, fungi prevailed over bacteria. Nevertheless, synergism was detected between both microorganism types for the mineralization of the aromatic hydrocarbons.     

Removal of H2S by co-immobilized bacteria and fungi biocatalysts in a bio-trickling filter

Biological control of odor gases has gained more attention in recent years. In this study, removal performance of a vertical bio-trickling filter inoculated with bacteria and fungi was studied. Bacteria and fungi were isolated from activated sludge in a sewage treatment plant. By adopting “three step immobilization method”, the bio-trickling filter could degrade pollutant immediately once hydrogen sulfide (H₂S) passed. The optimal empty bed resident time was 20 s. The optimal elimination capacity was about 60 g H₂S m^?3 h^?1 with removal efficiency of 95%. And the maximum elimination capacity was 170 g H₂S m^?3 h^?1. Pressure drop was ranged between 5 and 15 mm H₂O per bed over the whole operation. Removal efficiency was not affected obviously after terminating nutrient supply. The bio-trickling filter could recover back after shut down H₂S gaseous and liquid supplies simultaneously. Microbial community structure in the bio-trickling filter was not changed significantly.Combining bacteria and fungi would be a better choice for inoculation into a bio-trickling filter because of the quickly degradation of H₂S and rapid recovery under shut-down experiment. This is the first study attempting to combine bacteria and fungi for removal of H₂S in a bio-trickling filter.     

Simultaneous photocatalytic treatment of Cr(VI), Ni(II) and SDBS in aqueous solutions: Evaluation of removal efficiency and energy consumption

Simultaneous photocatalytic reduction of poisonous Cr(VI) and Ni(II) ions, coupled with photocatalytic oxidation of sodium dodecyl benzene sulfonate (SDBS) were studied with a trace amount of commercial titania nanoparticles and by means of a direct-photo-irradiation reactor. The co-presence of metal ions and SDBS causes metal ions reduction as well as SDBS oxidation to enhance and energy efficiency to improve. XRD, XPS and FTIR analysis were used to characterize TiO₂ particles before and after usage with the aim of evaluating the mechanism of reactions. The effect of major operating parameters, pH and temperature, was investigated. Under conditions of [Cr(VI)]₀ = [Ni(II)]₀ = 5 mg/L, [SDBS]₀ = 10 mg/L, [TiO₂] = 40 mg/L, pH 6 and T = 35 °C; the removal efficiencies of 55.4%, 71.2% and 57.2% were obtained, respectively, for Cr(VI) and Ni(II) reduction, as well as for SDBS oxidation, after 110 min operation. The relevant kinetic model jointed with the Arrhenius equation was introduced. Pseudo-first-order reactions are relevant. Energy consumption (electrical and thermal) evaluations revealed that operations at higher temperatures provide significant cost reduction. Meantime, a criterion was proposed for a consistent assessment of this kind of processes.     

Calorimetric behaviors of N2H4 by DSC and superCRC

The objective of this study is to obtain information about the thermal decomposition behaviors of hydrazine (N₂H₄) caused by metals, using differential scanning calorimeter (DSC) and SuperCRC. The DSC measurements revealed that the exothermic reactions of N₂H₄ were caused by the reaction conditions such as the type of cells; the T_DSC with a gold pan is 485.2 K and that with a glass capillary is 620.5 K. Besides, the activation energy of the thermal decomposition of N₂H₄, calculated from the Kissinger and Ozawa methods, were found to be about 38±2 kJ mol⁻¹ in the gold pan and 141±8 kJ mol⁻¹ in the glass capillary. Moreover, a heat flow profile was observed with SuperCRC during the mixing of N₂H₄ and the metal ion solution at 298 K. The maximum heat flow was related to the metal ion oxidative characters. The higher oxidative characters would provide a faster acceleration for the exothermic behavior than the lower oxidative ions. Based on this study, Mn(VII) and Cr(VI) were considered to exhibit strongly oxidative characteristics during mixing with N₂H₄.     

The electrocoagulation/flotation study: The removal of heavy metals from the waste fountain solution

The objective of this study was to investigate the possibility of heavy metals (copper, zinc and nickel) removal from the waste fountain solution by the electrocoagulation/flotation (ECF) treatment. After the printing process, the fountain solution changes its composition due to direct contact with different printing materials (plates, inks, etc.) and becomes enriched with metals. The effect of operational parameters, such as electrode materials and combinations, current density, interelectrode distance and operating time, was studied. Also, response surface methodology (RSM) was applied to evaluate the effect of main operational variables and to get a balanced removal efficiency of metals from waste fountain solution by ECF treatment. The iron/iron electrode combination yields a higher percentage of copper and zinc removal efficiency (>95% and >80%, respectively), while for nickel the aluminum/iron and iron/aluminum electrode combinations (>95 and >85%, respectively) proved to be more successful. The optimum interelectrode distance was 1.0 cm (for copper) and 1.5 cm (for zinc and nickel) for all current densities. Heavy metal removal efficiency increases with the increase of electrolysis time for all electrode combinations. Also, the increase of current density improves the ECF removal efficiency. Based on the results obtained through RSM, the optimized parameters for the ECF waste fountain solution treatment for metal removal were identified as: Fe(−)/Al(+) electrode with interelectrode distance of 1.5 cm, operating time of 60 min and current density of 8 mA cm⁻². Overall, the ECF treatment was proven very efficient in the removal of heavy metals from the waste fountain solution under optimum conditions.     

Zero valent nano-sized iron/clinoptilolite modified with zero valent copper for reductive nitrate removal

Nitrates constitute one of the main toxic contaminants of groundwater. On the other hand, groundwater may be considered anoxic (oxygen concentration less than 9 μg L^?1). This fact justifies the use of nano zero valent metals for nitrate removal. In such conditions, zero valent metals are quite stable against oxidation due to the very low level of dissolved oxygen concentration. It has been shown that the performance of zero valent iron coated clinoptilolite zeolite for the reduction of nitrate anion in un-buffered conditions may be enhanced by coating small amounts of Cu⁰ onto the freshly prepared Fe⁰/zeolite composite. An optimum loading of Cu⁰ exists for which the rate of nitrate removal is maximal. For this optimal composition, the nitrite anion production curve with time passes through a maximum. Nitrite production, however, is slightly higher for the Cu modified zeolite. It has been shown that the nitrate removal process is only slightly dependent on the initial solution pH. In the temperature range of 20–60 °C, the process is controlled by both the liquid phase mass transfer and intrinsic reaction rate resistances. FESEM analysis of the zero valent metal/zeolite composite showed that upon the metal reduction reaction, an egg-shell distribution of zero valent metal in the zeolite agglomerate particle is produced.     

Performance of a pilot scale up-flow septic tank for on-site decentralized treatment of residential wastewater

The aim of this research was to study the on-site anaerobic treatment of a medium-strength residential wastewater in a pilot-scale up-flow septic tank (UST). The effects of three different hydraulic retention times (HRTs) of 24, 12 and 6 h on the UST performance were investigated. The UST removed 85, 77, and 86% of biochemical oxygen demand (BOD₅), chemical oxygen demand (COD) and total suspended solids (TSS), respectively, at steady state operation and with a 24 h HRT. Decreasing the HRT to 12 and then 6 h resulted in deteriorated effluent quality and significantly reduced reactor performance. The sludge showed a high specific methanogenic activity (SMA) of 15.2 mL CH₄ g^?1 VSS d^?1 with raw wastewater substrate. The solids accumulated in the tank by the end of the experiment had a VSS/TSS of 0.57, demonstrating significant stabilization. Overall, the UST is concluded to be a technically and economically promising alternative to conventional septic tanks for the on-site decentralized treatment of residential wastewater, particularly in the rural communities of developing countries.     

Pb(II) adsorption from aqueous solutions by raw and treated biomass of maize stover – A comparative study

The potential to remove Pb(II) ion from wastewater treatment systems using raw and treated maize stover through adsorption was investigated in batch experiments. To achieve this, batch mode experiments were conducted choosing specific parameters such as pH (2–8), dosage concentration (2–30 g L⁻¹), contact time (5–180 min), temperature (20–45 °C) and metal ion concentrations (10–50 mg L⁻¹). Adsorption was pH-dependent showing a maximum at pH value 5. The equilibrium sorption capacities of raw and treated maize stover were 19.65 and 27.10 mg g⁻¹, respectively. The adsorption data fitted well to the Langmuir isotherm model. Kinetic studies revealed that the adsorption process followed pseudo-second-order model. The calculated thermodynamic parameters showed that the adsorption of Pb(II) was spontaneous and exothermic in nature. Consequently, this study demonstrated that both raw and treated maize stover could be used as adsorbents for the treatment of Pb(II) from industrial wastewaters.     

Growing Carbon Nanotube on Aluminum Oxides: An Inherently Safe Approach for Environmental Applications

Using micron-sized Al₂O₃ particles as carriers to grow carbon nanotubes (CNTs) under 700°C atmosphere of methane and hydrogen after pre-planted catalysts of Fe–Ni nanoparticles, those composite CNTs (CCNTs) have demonstrated several unique properties compared to CNTs—medium specific surface area and zeta potential, high adsorption capacity for metal ions, high recovery rate by acids, low decomposition heat for exothermal reaction, and so on. The adsorption behaviours of Pb²⁺, Cu²⁺ and Cd²⁺ in aqueous solutions by CCNTs are in good agreement with the Langmuir adsorption isotherm and second order kinetic model with maximum individual adsorption capacities of 67.11, 26.59 and 8.89 mg g⁻¹. The individual and competitive adsorption behaviours indicated that the preference order of adsorption were Pb²⁺ > Cu²⁺ > Cd²⁺ for aluminum oxides, activated carbon, commercial CNTs, and CCNTs as well as other researchers’ CNTs. We suggest that future development of CNTs to combine with metals and/or other materials, such as TiO₂, should consider attached to carriers or surface in order to avoid concerns on environment, health and safety. Thus, growing CNTs on Al₂O₃ particles to form CCNTs is an inherently safe approach for many promising environmental applications.     

Biosorption of zinc(II) on rapeseed waste: Equilibrium studies and thermogravimetric investigations

The removal of heavy metals from aqueous effluents so as to avoid their toxic, bioaccumulation and biomagnification effects to humans and environment is usually realized by means of physical, chemical treatment, and biological processes. The aim of this study is to evaluate the potential of rapeseed waste from biodiesel production as a biosorbent for Zn(II) ions.The ability of the rapeseed waste for Zn(II) biosorption exhibited a maximum at pH 4.5–5. The removal efficiency of Zn(II) from solution with an initial concentration of 72 mg L⁻¹ varied from 39% to 89% for an increase of the rapeseed waste dose from 2 to 30 g L⁻¹. The amount of Zn(II) retained on the tested rapeseed increased with increasing metal ion concentration, but the Zn(II) sorption percentage decreased. The equilibrium data are fitted to the Langmuir isotherm better than to the Freundlich isotherm. The kinetics of Zn(II) biosorption process follows a pseudo-second order model. The thermal stability of the rapeseed before and after Zn(II) biosorption was studied by thermogravimetric analysis. It was found that the zinc loaded rapeseed exhibits a better initial thermal stability than the original rapeseed, presumably due to the cross linking generated by the intermolecular complexation of Zn(II) ions. In both cases, the thermal decomposition takes place according to some reassembling kinetic models, in two phases with order n reactions. The results of this study strongly suggest the possibility to use rapeseed as an effective biosorbent for Zn(II) ions removal from aqueous effluents (municipal/industrial wastewaters).