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.     

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.     

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.     

Adsorption of copper and nickel on Na-bentonite

The removal of copper and nickel from aqueous solution on the Na-bentonite has been studied under static conditions. Experiments were carried out as a function of solution pH, dosage of Na-bentonite, contact time and temperature. The adsorption equilibrium for nickel and copper onto Na-bentonite is reached in 200 min. The adsorption of copper and nickel is pH dependent in the pH range 2–9. The kinetic process of adsorption can be described by the pseudo-second-order kinetic equation excellently and the adsorption isotherm be fitted to the Langmuir model by means of regression analyses very well. The adsorption capacities follow the order of Cu²⁺ > Ni²⁺ in single-component systems and competitive adsorption capacities in order decreasing is Cu²⁺ > Ni²⁺ in binary-component systems.     

Characterization of heavy metals in fly ash from municipal solid waste incinerators in Shanghai

This study aims to develop a methodology for analysis of characteristics of heavy metals in MSWI fly ash. It performed analysis of composition of heavy metals, leaching toxicity, leaching behavior as a function of pH, specification distribution and corresponding mineral components of residue derived from each step of the sequential extraction. It is found that content of heavy metals follows the sequence of Zn > Pb > Cu > Cr > As > Ni > Cd approximately Hg in both plants, and that total heavy metals account for less than 1% by mass of fly ash. Major hazardous heavy metals in fly ash are As, Cd, Hg, Pb and Zn, whose leaching ratios exceed the limit value described in hazardous waste identification standard. Measured leaching results of Cu, Pb and Zn are essentially consistent with the simulated results at pH between 0 and 13. Content of calcium-silicates, alumino-silicates and glass phases in residue derived from sequential extraction procedure increases steadily from the first step to the fifth step of the sequential extraction procedure. Cu, As, Cr, Hg, Cd, and Ni, relatively stable under strong basic conditions, can be leached out under strong acidic conditions, while Zn and Pb tend to be leached out under both strong acidic and basic conditions.     

Artificial neural network modelling of As(III) removal from water by novel hybrid material

The present study reported a method for removal of As(III) from water solution by a novel hybrid material (Ce-HAHCl). The hybrid material was synthesized by sol–gel method and was characterized by XRD, FTIR, SEM–EDS and TGA–DTA. Batch adsorption experiments were conducted as a function of different variables like adsorbent dose, pH, contact time, agitation speed, initial concentration and temperature. The experimental studies revealed that maximum removal percentage is 98.85 at optimum condition: pH = 5.0, agitation speed = 180 rpm, temperature = 60 °C and contact time = 80 min using 9 g L⁻¹ of adsorbent dose for initial As(III) concentration of 10 mg L⁻¹. Using adsorbent dose of 10 g L⁻¹, the maximum removal percentage remains same with initial As(III) concentration of 25 mg L⁻¹ (or 50 mg L⁻¹). The maximum adsorption capacity of the material is found to be 182.6 mg g⁻¹. Subsequently, the experimental results are used for developing a valid model based on back propagation (BP) learning algorithm with artificial neural networking (BP-ANN) for prediction of removal efficiency. The adequacy of the model (BP-ANN) is checked by value of the absolute relative percentage error (0.293) and correlation coefficient (R² = 0.975). Comparison of experimental and predictive model results show that the model can predict the adsorption efficiency with acceptable accuracy.     

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).     

Rotating biological contactors for wastewater treatment – A review

Rotating biological contactors (RBCs) for wastewater treatment began in the 1970s. Removal of organic matter has been targeted within organic loading rates of up to 120 g m⁻² d⁻¹ with an optimum at around 15 g m⁻² d⁻¹ for combined BOD and ammonia removal. Full nitrification is achievable under appropriate process conditions with oxidation rates of up to 6 g m⁻² d⁻¹ reported for municipal wastewater. The RBC process has been adapted for denitrification with reported removal rates of up to 14 g m⁻² d⁻¹ with nitrogen rich wastewaters. Different media types can be used to improve organic/nitrogen loading rates through selecting for different bacterial groups. The RBC has been applied with only limited success for enhanced biological phosphorus removal and attained up to 70% total phosphorus removal. Compared to other biofilm processes, RBCs had 35% lower energy costs than trickling filters but higher demand than wetland systems. However, the land footprint for the same treatment is lower than these alternatives. The RBC process has been used for removal of priority pollutants such as pharmaceuticals and personal care products. The RBC system has been shown to eliminate 99% of faecal coliforms and the majority of other wastewater pathogens. Novel RBC reactors include systems for energy generation such as algae, methane production and microbial fuel cells for direct current generation. Issues such as scale up remain challenging for the future application of RBC technology and topics such as phosphorus removal and denitrification still require further research. High volumetric removal rate, solids retention, low footprint, hydraulic residence times are characteristics of RBCs. The RBC is therefore an ideal candidate for hybrid processes for upgrading works maximising efficiency of existing infrastructure and minimising energy consumption for nutrient removal. This review will provide a link between disciplines and discuss recent developments in RBC research and comparison of recent process designs are provided (Section 2). The microbial features of the RBC biofilm are highlighted (Section 3) and topics such as biological nitrogen removal and priority pollutant remediation are discussed (Sections 4 Biological nutrient removal in RBCs, 5 Priority pollutant remediation in RBCs). Developments in kinetics and modelling are highlighted (Section 6) and future research themes are mentioned.     

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.     

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.     

Continuous nitrifying granular sludge bioreactor: Influence of aeration and ammonium loading rate

Granulation of nitrifying bacteria was investigated in a continuous bubble column bioreactor. Then, the combined effect of aeration and ammonium loading rates on dissolved oxygen (DO) concentration as well as nitrification process was evaluated in the system using an experimental design technique. After 120 days, stable nitrifying granules with average diameter of 1.4 mm and settling velocities of 55 m/h were obtained. The influence of increasing ammonium loading rate (ALR) was found to be more significant than decreasing aeration rate on the reduction of DO concentration inside the nitrifying bioreactor. The system could handle the ALR values of 0.48–1.92 gNH₄⁺-N/L d with the ammonium removal efficiency from 65% to nearly 100% at the tested airflow rates of 2.5 and 4.5 L/min. At the low aeration, the complete ammonium conversion to nitrate was replaced with nitrite when the ALR increased to 1.44 gNH₄⁺-N/L d. At the high aeration, however, almost complete nitrification was achieved except the high ALR in which the nitrite accumulation was observed up to 38%. The study demonstrated that the continuous bioreactor had a considerable performance for obtaining stable nitrifying granules to have nitrite accumulation under control with changing the ratio of aeration rate and ALR.     

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.     

Use of advance oxidation process to improve the biodegradability of olive oil mill effluents

In this study, recalcitrant total phenol (TPh) and organic matter removal were investigated at olive mill wastewater (OMW) in sequential Coagulation and Fenton system. This study focused on different operational parameters such as pH, H₂O₂, and Fe²⁺ dosages, and [Fe²⁺]/[H₂O₂] ratios. The optimum conditions were determined as; pH = 3; [Fe²⁺] = 2.5 g/L; [Fe²⁺]/[H₂O₂] = 2.5. A higher treatment efficiency was achieved at sequential Coagulation and Fenton system (COD, 65.5%) and TPh, 87.2%), compared to coagulation process (COD, 51.4%; total organic carbon (TOC), 38.6% and total nitrogen (TN) 52.1%). This study demonstrated that the Coagulation and Fenton process has a potential for efficient removal of phenolic pollutants from wastewater.     

Acid-enhanced limestone defluoridation in column reactor using oxalic acid

Acid enhanced limestone defluoridation of water has been studied in a crushed limestone column reactor using oxalic acid (OA). The defluoridation has been studied with varying initial fluoride concentrations of 5, 10, 15 and 20 mg/L and acid concentrations of 0.01, 0.05 and 0.1 M. The fluoride removal was found to increase with increase in the concentration of the acid, removing fluoride up to 95% with 0.1 M OA. The observed good fluoride removal has been attributed to a combination of two mechanisms of fluoride removal, viz., precipitation of calcium fluoride and adsorption of fluoride ions on limestone surfaces. While the removal by precipitation remains same on repeated use of the same limestone column, the adsorption is more with the fresh limestone and decreases gradually on repeated use of the same limestone column. The precipitate has been characterized using various analytical tools, viz., X-ray diffraction, IR spectroscopy, thermogravimetric analysis, scanning electron microscopy combined with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The Ca²⁺ ions, formed due to dissolution of limestone by the acid, precipitate calcium fluoride along with precipitation of calcium oxalate. A good fluoride removal ability, low residual oxalate, acceptable final pH, low-cost and simplicity of the process make the present acid-enhanced limestone defluoridation process with OA a potential method for defluoridation of groundwater.     

On–off control of aeration time in the simultaneous removal of ammonia and manganese using a biological aerated filter system

The biological aerated filter (BAF) system, a new alternative in drinking water treatment, was designed to remove NH₄⁺–N and Mn²⁺ simultaneously. This study aimed to control the aeration time in the BAF system for simultaneous NH₄⁺–N and Mn²⁺ removal to achieve the Malaysian effluent quality regulation for drinking water. The experiment was conducted under four strategies of S1, S2, S3 and S4. The results demonstrated that acceptable levels of NH₄⁺–N and Mn²⁺ were achieved over a 6 h aeration period (S1), producing effluent concentrations of 0.7 mg/L (93.2% removal) and 0.08 mg/L (79.6% removal), respectively. At the initial treatment of S1 and S2, the dissolved oxygen (DO) level rapidly increased until it reached a saturated concentration (6.8 mg/L DO) after 2 h period. Automatic on–off aeration time to maintain 3 mg/L DO set point (S4) resulted with a good effluent quality of NH₄⁺–N and Mn²⁺ compared with the 2 mg/L DO set point (S3) which did not meet the regulated standard limits. Through the automatic on–off aeration time, the saturated and excessive DO levels in the BAF system can be avoided consequently reduce the wastage of energy and electrical consumption for simultaneous NH₄⁺–N and Mn²⁺ removal from drinking water treatment.     

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.     

Evaluating the efficacy of alumina/carbon nanotube hybrid adsorbents in removing Azo Reactive Red 198 and Blue 19 dyes from aqueous solutions

Concerning the high volume of wastewater containing dye in Iran and its adverse effects, it is necessary to develop scientific solutions for treating these wastewaters. The aim of this study was to evaluate the efficiency of the alumina-coated multi-walled carbon nanotubes in removing the Reactive Red 198 (RR 198) and Blue 19 (RB 19) dyes. Synthetic samples including dye with different concentrations were prepared. These samples were put in contact with different contents of alumina/multi-walled carbon nanotubes, in different pH values, in different contact times, different temperatures and the presence of sodium sulfate or sodium carbonate. The optimum pH, dye concentration and temperature for removal of the two dyes was 3, 50 mg l⁻¹ and 25 °C, respectively. The optimum adsorbent dose for removal the RR 198 dye was 0.5 g l⁻¹ and for Blue 19 was 0.4 g l⁻¹. The optimum contact time for RR 198 was 150 min and RB 19 was 180 min. In this condition, maximum removal efficiency for RR 198 and RB 19 was 91.54% and 93.51%, respectively. The adsorption study was analyzed kinetically, and the results revealed that the adsorption fitted a pseudo-second order kinetic model. According to these results alumina/multi-walled carbon nanotubes can effectively remove RR 198 and RB 19 from aqueous solutions.     

Effects of high ammonia loads on nitrogen mass balance and treatment performance of a biotrickling filter

A biotrickling filter packed with coal slag as packing medium was continuously used for more than 9 months under high ammonia loading rates of up to 140 g/m³/h. Nitrogen mass balance and microbial community analysis were conducted to evaluate the inhibitory effects of high ammonia concentration and metabolic by-products on the rates of nitrification. Ammonia removal efficiency reached above 99% at an empty bed retention time of as low as 8 s when inlet concentrations were below 350 ppm. The maximum and critical elimination capacities of the biotrickling filter were 118 g/m³/h and 108.1 g/m³/h, respectively. Kinetics analysis results showed that less than 2.5 s was required for the biotrickling filter with pH control to treat ammonia at concentrations of up to 500 ppm in compliance with the Taiwan EPA standard (outlet NH₃ < 1 ppm). Results of mass balance and microbial community analysis indicated that complete removal was mainly contributed by the activities of autotrophic ammonia oxidizing bacteria and not by physical absorption or adsorption at low loading rates. However, at high inlet loadings, ammonium became the dominant by-product due to inhibitory effects of high ammonia concentration on the bacterial community.     

Achieving stable partial nitritation using endpoint pH control in an SBR treating landfill leachate

The feasibility of using endpoint pH control to achieve stable partial nitritation (PN) in an SBR for landfill leachate treatment was investigated. By imposing a fixed-time anoxia followed by variable-time aeration in an SBR cycle, successful partial nitritation was maintained for 182 days at a nitrogen loading rate of 0.30–0.89 kg/m³/day. The effluent NO₂⁻-N/NH₄⁺-N ratio and the effluent NO₃⁻-N concentration were 1.30 ± 0.22 and 16 ± 9 mg/L, respectively. High free ammonia (FA) and low dissolved oxygen (DO) concentrations were inhibition factors of nitrate formation. The termination of aeration at a suitable endpoint pH was the key to achieve an effluent NO₂⁻-N/NH₄⁺-N ratio close to the stoichiometric value. This endpoint pH control strategy represents practical potentials in the engineered application of combined PN–ANAMMOX processes.