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.     

Improved VOC bioremediation using a fluidized bed peat bioreactor

A gas–solid fluidized bed bioreactor was successfully used to treat air contaminated with a volatile organic compound (VOC). A bioreactor containing both a fluidized and packed bed of moist peat granules removed ethanol, a representative VOC, from an air stream. The fluidized bed operation mode of the bioreactor outperformed the packed bed mode. The maximum elimination capacity (EC) of ethanol in the fluidized mode was 1520 g m⁻³ h⁻¹, with removal efficiencies ranging between 45 and 100%, at loadings up to 3400 g m⁻³ h⁻¹. Maximum EC was 530 g m⁻³ h⁻¹ in the packed bed mode. Removal efficiency in the fluidized bioreactor was best at the lowest velocity, where the bubbling bed fluidization regime predominated. As gas velocity increased, the size and amount of large bubbles (slugs) increased and removal efficiency decreased while elimination capacity increased.     

Two-stage biodegradation coupled with ultrafiltration for treatment of municipal landfill leachate

The municipal landfill leachate was treated in a hydrolysis–acidification reactor (HAR)/aerobic bio-contact oxidation reactor (ABOR) following a pretreatment with ultrafiltration (UF) membrane. Experiments were conducted continuously for 44 days at a constant flow rate of 20 l d⁻¹ and organic loading rates (OLRs) from 0.75 to 1.5 kgCOD m⁻³ per day. The results showed that COD of the leachate steadily decreased from 20,015 mg l⁻¹ to less than 3000 mg l⁻¹, and NH₄-N decreased from 368.6 mg l⁻¹ to 259.3 mg l⁻¹ in the UF process. The COD and NH₄-N removal efficiency of HAR was 56.7% and 27.7%, and that of ABOR was 94.6% and 86.7%, respectively. The total COD and NH₄-N removal efficiency reached 99.6% and 93.2%, respectively. UF and HAR played a critical role in raising the biodegradability of the landfill leachate, while ABOR had an important function on removing the dissolved NH₄-N in leachate.     

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.     

Nanofiltration of concentrated and salted tuna cooking juices

Tuna cooking juice from a Tunisian tuna-processing unit has a high level of polluting load: chemical oxygen demand (COD) is comprised between 4 and 20 g L⁻¹, nitrogen kjedahl (NK) between 0.6 and 3 g L⁻¹ and dry matter between 120 and 160 g L⁻¹. The juice has thus to be treated before being rejected into the environment. This paper considers the nanofiltration (NF) of these concentrated organic/inorganic mixtures using an AFC 30 (NF) membrane. The work focusses on the effect of organic and inorganic matters on the permeate flux and rejections of these matters. For this purpose, mixtures of salt and organic pollution (COD), used as model solutions, were prepared by the dilution of a typical industrial tuna cooking juice. The permeate flux was found to decrease when salt and organic matter concentrations increase. The recovery rate in organic matter decreases with increasing salt or organic matter content and the recovery rate of salt decreases when the COD concentration increases.     

Absorption kinetics of NO from simulated flue gas using Fe(II)EDTA solutions

The absorption of NO encountering flue gases in aqueous solutions of Fe(II)EDTA was determined using a semi-batch stirred tank with a plane gas–liquid interface at 50 °C. The concentrations of NO, SO₂ and O₂ in the feeding stream were 300–800 ppm, 500–2200 ppm and 0–20%, respectively. The pH value of the Fe(II)EDTA solutions varied from 3 to 11. The concentrations of Fe(II)EDTA were maintained between 0.01 and 0.05 M. Experiments were performed to evaluate the effect of operating parameters on the NO absorption rate, the reaction kinetics of the reactants in gas and liquid phases, and the effect of competition between various reactants on the mass transfer rate in the NO removal system. Results indicate that the average reaction rate constant is 3.70 × 10⁷ M⁻¹ s⁻¹. Adding NaOH does not increase the absorption capability of Fe(II)EDTA. The presence of O₂ decreases the NO absorption rate with Fe(II)EDTA. The absorption rate of NO with Fe(II)EDTA decreases at low concentrations of SO₂, but increases at high concentrations.     

Removal of Zn and Ni by adsorption in a fixed bed of wheat straw

Zn⁺² and Ni⁺² in a solution were removed by biosorption in a fixed bed of wheat straw Triticum aestivum. The removal rate and the mass transfer coefficient for Zn⁺² and Ni⁺² were found to be proportional to the liquid superficial velocity to the power of 0.31 for the range of the particle Reynolds number from 18 to 445 (equivalent liquid rates of 0.00070–0.0175 m³ m⁻² s⁻¹). This agrees well with reported literature for mass transfer in a packed bed of solid particles under a laminar flow regime. Effect of the solution pH, temperature and the particle size (0.5, 1.0, 1.5 and 2.0 in.) on biosorption of Zn⁺² and Ni⁺² was also investigated. Biosorption of both Zn⁺² and Ni⁺² increased significantly with the solution pH from 4.0 to 7.0. On the other hand, Zn⁺² and Ni⁺² removal appeared to be insensitive to liquid temperature from 25 to 30 °C. Nevertheless, a 25% increase in the percentage removal of metal ions was observed with further increase of liquid temperature from 30 to 35 °C. However, the biosorbent particle size did not seem to have a systematic effect on the biosorption of Zn⁺² and Ni⁺². In addition, biosorption of Zn⁺² was not affected considerably by co-adsorption of the bimetal solution while biosorption of Ni⁺² decreased about 14%.     

Removal of humic substances from landfill leachate by Fenton oxidation and coagulation

In this study, chemical oxygen demand (COD) was characterized as total organic constituents and the isolated humic substances (HS) were characterized as an individual organic contaminant in landfill leachate. It was found that the HS content of landfill leachate was 83.3%. The results of laboratory tests to determine the roles of HS in reducing the organic content of landfill leachate during Fenton process are presented. Furthermore, the performances of oxidation and coagulation of Fenton reaction on the removal of HS and COD from leachate were investigated. The change curves of HS removal were similar to those of COD. The HS removal was 30% higher than COD removal, which indicated that HS were mostly degraded into various intermediate organic compounds but not mineralized by Fenton reagent. The oxidation removal was greatly influenced by initial pH relative to the coagulation removal. The oxidation and coagulation removals were linear dependent with hydrogen peroxide and ferrous dosages, respectively. Ferrous dosage greatly influenced the coagulation removal of COD at low ratio ([H₂O₂]/[Fe²⁺] < 3.0), but not at extremely high ratio ([H₂O₂]/[Fe²⁺] > 6.0). The coagulation removal of HS was not affected obviously by oxidation due to both Fenton oxidation and coagulation remove high molecular weight organics preferentially. Higher temperature gave a positive effect on oxidation removal at low Fe²⁺ dosage, but this effect was not obvious at high Fe²⁺ dosage.     

High nitrite accumulation and strengthening denitrification for old-age landfill leachate treatment using an autocontrol two-stage hybrid process

An autocontrol two-stage hybrid process was developed to treat landfill leachate. Biological nitrogen removal with nitrification and denitrification via nitrite pathway was split into two stages. The first stage was designed for the high nitrite accumulation and was composed of two hybrid bed reactors (Hybrid I and Hybrid II) and a coagulation–flocculation reactor having effective volumes of 120 L and 80 L, respectively. The second stage was designed for strengthening denitrification and included a single 80 L reactor. The carriers of the hybrid bed reactors were composed of fixed multiple flexible carriers and suspended particle carriers. Dissolved oxygen (DO), pH value, oxidation–reduction potential (ORP) and temperature were used as online fuzzy control parameters of the automatic control system. The concentration of nitrite in Hybrid I and Hybrid II could reach 411 mg L⁻¹ and 604 mg L⁻¹, respectively. Ammonia removal has reached maximal rates of 0.061 kgNH₄⁺-N (m³ h)⁻¹ and 0.041 kgNH₄⁺-N (m³ h)⁻¹, respectively. A maximum nitrite removal rate of 0.211 kgNO₂⁻-N (m³ h)⁻¹ was observed during the strengthening denitrification. The running time of one cycle was not fixed and was actually controlled by the system. The results indicated that the running period was more closely related to influent ammonia concentration than influent COD concentration. The aeration times could be shortened and the energy could be saved. The autocontrol two-stage hybrid process is therefore an economical and effective way for landfill leachate treatment.     

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.     

Study into influence of different types of igniters on the explosion parameters of dispersed nitrocellulose powder

Nitrocellulose is a flammable compound produced by cellulose nitration. The nitrocellulose production and handling are associated with a risk of fire and explosion. Nitrocellulose is used as either collodion cotton (<12.5% N) or as an explosive (>12.5% N). Nitrocellulose is a fibrous or powdered substance and may detonate or burn upon certain conditions. The article compares the combustion parameters of dry nitrocellulose in the KV-150M2-UIBE explosion chamber at the concentrations of 250, 500 and 750 g m⁻³. To ignite a nitrocellulose sample, six different types of igniters were used. A commercially available 5 kJ pyrotechnic igniter was used as the standard. Also used were a nitrocellulose igniter, a pyrotechnic igniter with magnesium powder and KNO₃/KClO₃, and an exploding wire (Kanthal and tungsten wire). The examined igniters were found to affect the explosion parameters of dispersed nitrocellulose. The deviation of the explosion constant K_st reached 50% of the standard value. The highest pressure of 12.73 bar g was reached at a concentration of 750 g m⁻³ and an igniter exploding wire with Kanthal wire. The highest K_st value of 287.9 bar.m.s⁻¹ was achieved at a concentration of 750 g m⁻³, when using the pyrotechnic igniter with KClO₃ and magnesium powder.     

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.     

Disintegration of waste activated sludge by different applications of Fenton process

Oxidative disintegration of municipal waste activated sludge (WAS) using conventional Fenton (Fe²⁺ + H₂O₂, CFP) and Fenton type (Fe⁰ + H₂O₂, FTP) processes was investigated and compared in terms of the efficiency of sludge disintegration and enhancement of anaerobic biodegradability. The influences of different operational variables namely sludge pH, initial concentration of Fe²⁺ or Fe⁰, and H₂O₂ were studied in detail. The optimum conditions have been found as catalyst iron dosage = 4 g/kg TS, H₂O₂ dosage = 40 g/kg TS and pH = 3 within 1 h oxidation period for both CFP and FTP. Kinetics studies were performed under optimal conditions. It was determined that the sludge disintegration was happened in two stages by both processes: rapid and subsequent slow disintegration stages and rapid sludge disintegration stage can be described by a zero-order kinetic model. The effects of oxidative sludge disintegration under the optimum conditions on anaerobic digestion were experienced with biochemical methane potential (BMP) assay in batch anaerobic reactors. Total methane production in the CFP and FTP pre-treated reactors increased by 26.9% and 38.0%, relative to the untreated reactor (digested the raw WAS). Furthermore, the total chemical oxygen demand reductions in the pre-treated reactors were improved as well.     

Synthesis of CuO nanoparticles through green route using Citrus limon juice and its application as nanosorbent for Cr(VI) remediation: Process optimization with RSM and ANN-GA based model

In present investigation, an attempt has been made for the synthesis of cupric oxide nanoparticles (CuONPs) through a green route by utilizing lemon juice extract as a bioreductant. The synthesized CuONPs were characterized through UV–visible spectroscopy, Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The CuONPs were utilized for Cr(VI) removal from water through adsorption method in batch mode at different initial Cr(VI) concentration, pH, temperature and CuONPs dosage. The maximum uptake capacity of CuONPs was found to be 16.63 mg of Cr(VI)/g at pH 4.0. Implementation of response surface methodology (RSM) followed by artificial neural network hybridized with genetic algorithm (ANN-GA) approach has resulted maximum Cr(VI) adsorption of 98.8% under the optimized conditions of initial metal concentration 22.5 mg/L, pH 3.81, CuONPs dose 1.28 g/L and temperature 37.1 °C. Under optimum conditions, adsorption isotherm study was conducted, which showed that the fitness of experimental data was well achieved with Langmuir isotherm model illustrating monolayer pattern of adsorption. Thermodynamic study revealed that the process was spontaneous and endothermic in nature, while adsorption kinetics was best explained by pseudo-second order kinetic model.     

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.     

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.     

Toluene removal biofilter modeling: Optimization and case study

Based on the model proposed by De Visscher and Van Cleemput for methane oxidation in landfill cover soils, a simulation model for biofiltration of toluene-contaminated air has been developed for biofilters with substrate inhibition. A convenient way to optimize biofilter performance was developed assuming Haldane kinetics. It was calculated that for a typical oilsands operation emitting 200 ton of toluene annually, 90% of the toluene can be removed by a 740 m³ biofilter, if the waste gas sent to the biofilter has a toluene concentration of 2.25 g m⁻³. The optimal initial concentration increases with increasing target efficiency.     

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.     

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.     

Using soybean isoflavone to prevent hydrogen production reaction of aluminium dust and water in wet dust removal systems

Using a dry dust removal system used for aluminium dust collection presents a dust explosion risk, whereas a wet dust removal system presents a risk of hydrogen fire and explosion. Neither system can attain a sufficient level of safety for use at aluminium processing sites. In this paper, soybean isoflavone, a non-toxic and environmentally sustainable flavonoid, was investigated to inhibit hydrogen production from aluminium dust and water. Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and Fourier transform infrared spectroscopy (FTIR) were used to characterize aluminium particles before and after the reaction. Soybean isoflavone was found to inhibit hydrogen production from aluminium dust and water. At a soybean isoflavone solution concentration of 2.1 g L⁻¹, a dense protective film resulting from chemical adsorption on the surfaces of the aluminium particles isolated the aluminium particles from water molecules. This film blocked the reaction pathway between the aluminium particles and water to suppress hydrogen generation. This fundamental study addresses the problems of hydrogen fires and explosions in wet dust removal systems for aluminium dust collection and provides a novel, safe and effective method for aluminium dust removal.