A study of the photocatalytic degradation of metamitron in ZnO water suspensions

The photocatalytic degradation of the herbicide metamitron in water using ZnO under Osram ULTRA-VITALUX® lamp light was studied. The effect of the operational parameters such as initial concentration of catalyst, initial metamitron concentration, initial salt concentration (NaCl, Na₂CO₃ and Na₂SO₄) and pH was studied. The optimal concentration of catalyst was found to be 2.0 g/l. First-order rate constants were calculated for the uncatalysed reactions. On the base of the Langmuir-Hinshelwood mechanism, a pseudo first-order kinetic model was illustrated and the adsorption equilibrium constant and the rate constant of the surface reaction were calculated (0.119 l mg^− 1 and 0.836 mg l^− 1 min^− 1, respectively). The photodegradation rate was higher in acidic than in alkaline conditions. When salt effect was studied, it was found that sodium carbonate was the most powerful inhibitor used, while sodium chloride was the weakest one. A negligible inhibition was observed when the concentration of sodium chloride was 20 mM.The rate of photodecomposition of metamitron was measured using UV spectroscopy and HPLC, while its mineralization was followed using ion chromatography (IC), as well as total organic carbon (TOC) and total nitrogen (TN) analysis.Under the employed conditions, almost complete disappearance of 9 mg/ml of herbicide, 56% TOC and 34% TN removal, occurred within 4 h. The ion chromatography results showed that the mineralization led to ammonium, nitrite and nitrate ions during the process.     

Phosphorus recovery from centralised municipal water recycling plants

Depletion of world phosphorus reserves is driving research into options to recover and recycle this essential, non-renewable resource. Phosphate (PO₄³⁻) recovery at centralised wastewater treatment plants can be achieved through biosolids reuse or sidestream precipitation though the PO₄³⁻ levels are low compared with decentralised systems based on source separation. However, the recent growth in membrane based water recycling projects, where reverse osmosis is used to produce high quality water has resulted in the production of liquid waste streams with elevated concentrations of PO₄³⁻. Four recycling scenarios using different membrane processes and anaerobic treatment were compared and the potential PO₄³⁻ recovery via struvite (magnesium ammonium phosphate) from membrane concentrate examined. By incorporating an anaerobic reactor in the process we have been able to investigate the possibility of cogeneration of electricity from methane. Modelling of struvite recovery from membrane concentrate with co-generation indicates a net power requirement of 260 kWh/kg P recovered compared with 510 kWh/kg P for a system without cogeneration at a water consumption level of 250 L/p/d. When water consumption is limited to 80 L/p/d, this scenario compares favourably with literature values for recovery from source separated urine which range from 18 to 43 kWh/kg P.     

Solubility of blue CoAl2O4 ceramic pigments in water and diethylene glycol media

The chemical stability of blue CoAl₂O₄ ceramic pigment in aqueous and non-aqueous suspension was investigated. Distilled water and diethylene glycol (DEG) were used as media. The isoelectric points (IEP) for the commercial and synthesised CoAl₂O₄ pigment were determined to be 4.9 and 8.5, respectively. The IEP shifts toward acidic pH values for the commercial pigment with respect to the synthesised pigment due to the existence of the quartz phase. In water, the cobalt ion concentration was low (2.5 mg dm⁻³), and this concentration did not change with time. However, the aluminium ion concentration was initially high and then decreased to ∼10 mg dm⁻³ at pH 9 and 11 due to the precipitation of Al³⁺ ions as an Al(OH)₃ phase. In DEG, the dissolution of pigment particles with higher ion concentrations (>800 mg dm⁻³) was more significant than that of the aqueous medium, implying that CoAl₂O₄ pigment has insufficient chemical stability in DEG medium with respect to aqueous suspensions.     

Development of a four-grade and four-segment electrodialysis setup for desalination of polymer-flooding produced water

An electrodialysis (ED) setup with an 11 m³/h water treatment scale was designed based on a small experimental device. The setup adopts four-grade and four-segment (four-GS) reversal electrodialysis (EDR) technology to desalinate polymer-flooding produced water (PFPW). The removal rate of total dissolved solids (TDS) with different flow rates was measured with different grades and segments. The operating performance of this setup was determined to meet design standards. The maximum treatment capacity and the optimal operation conditions of the tested setup were studied. The design standards were met only by adopting a four-GS ED setup. The maximal capacity of the four-GS ED setup for treating PFPW was 5 m³/h. The optimal operating condition and results were at an operating electric current of 86 A, 62.5% production rate of diluted treated PFPW, 0.89 kW?h/m³ energy consumption, and 78.7% TDS removal rate. Under optimal conditions, the treated PFPW has two beneficial uses. First, the diluted treated PFPW is feasible for preparing polymer solutions. Second, the concentrated treated PFPW is feasible for replacing the original PFPW as the injecting water in the water-flooding process for high permeability layers.     

Equilibrium and kinetic modelling of the adsorption of Cd ions onto chestnut shell

A study on the removal of Cd²⁺ ions from aqueous solutions by acid formaldehyde pretreated chestnut (Castanea sativa) shell was conducted in batch conditions. The influence of different parameters: adsorption time, temperature (15, 25 and 35 °C) and initial concentration of Cd²⁺ ions (15.3, 50.5 and 87.3 mg L^− 1), on cadmium uptake was analysed. Cadmium free and cadmium loaded chestnut shell were characterized by FTIR spectroscopy, which evidenced the functional groups involved in cadmium uptake. Cadmium adsorption equilibrium could be described by the Freundlich adsorption model at all the temperatures essayed, which predicted shell heterogeneity. The Cd²⁺ adsorption process by chestnut shell followed the pseudo second order kinetic model. Cadmium sorption capacity increased with decreasing temperature at an initial concentration of 15.3 mg L^− 1 and with increasing initial cadmium concentration at a temperature of 25 °C. The second order kinetic constant, which increased with increasing temperature, was used to calculate the energy of adsorption as equal to 19.2 kJ mol^− 1.     

Nanofiltration and reverse osmosis thin film composite membrane module for the removal of dye and salts from the simulated mixtures

Nanofiltration (NF) and reverse osmosis (RO) thin film composite polyamide membrane modules were used to remove the color from the contaminated solution mixture. The feasibility of membrane processes for treating simulated mixture by varying the feed pressures (100-400 psi) and feed concentrations was studied to assess the separation performance of both NF and RO membranes. It was found that the efficiency of NF and RO membranes used in the treatment of colored water effluents was greatly affected by the presence of salts and dyes in the mixture. Color removal by NF with a high rejection of 99.80% and total dissolved solids (TDS) of 99.99% was achieved from RO by retaining significant flux rate compared to pure water flux, which suggested that membranes were not affected by fouling during the simulated wastewater process operation. The effect of varying concentrations of Na₂SO₄ salt and methyl orange (MO) dye on the performance of spiral wound membranes was determined. Increasing the dye concentration from 500 to 1000 mg/L resulted in a decrease of salt rejection at all operating pressures and for both concentrations of 5000 and 10,000 mg/L as the feed TDS. Increasing the salt concentration from 5000 to 10,000 mg/L resulted in a slight decrease in dye removal.     

Synthesis, structural and magnetic properties of nanostructured Ca0.9Gd0.1MnO3 obtained by modified glycine nitrate procedure (MGNP)

Ca_0.9Gd_0.1MnO₃ nanopowders with perovskite type crystal structure were synthesized by modified glycine nitrate procedure. Nanopowders were prepared by combining glycine with metal nitrates and/or metal acetates in their appropriate stoichiometric ratios. Modification of the procedure was performed by partial replacement of nitrates by acetates, in order to control the burn-up reaction. Obtained Ca_0.9Gd_0.1MnO₃ powders were calcinated in the temperature interval from 850 °C to 950 °C for 10 min. Properties such as phase evolution, lattice parameters, chemical composition and magnetic properties were monitored by DTA, X-ray diffraction, SEM/EDS and magnetic measurements. Magnetic measurements performed at the sample with the smallest crystallite size showed that a 10% of Gd³⁺ substituted Ca²⁺ ions changes antiferromagnetic properties of CaMnO₃ by the introduction of ferromagnetic interaction due to a double exchange between Mn³⁺ and Mn⁴⁺ ions. Presence of competing interactions and their randomness lead to a formation of a spin glass state below Neel temperature T_N = 110 K. From the high temperature magnetic susceptibility measurements effective magnetic moment of manganese ions is determined which lies between the values for Mn³⁺ and Mn⁴⁺ ions.     

Flat-plate submerged membrane bioreactor for the treatment of higher-load graywater

Graywater treatment has been the focus when topics of decentralized treatment systems are discussed. In this paper, the treatment of higher-load graywater, a mixture of washing machine and kitchen sink wastewater, was investigated. A 10 L lab-scale submerged membrane bioreactor (subMBR) was operated with a flat-plate membrane for 87 days. Permeate was intermittently withdrawn at constant transmembrane pressure (TMP) induced by water level difference and without pump requirement. The pollutants' removal and membrane behavior were monitored. The COD removal was around 96% and a permeate COD of about 26 mg L^− 1 was obtained. The total linear alkylbenzene sulfonate (LAS) removal achieved was > 99%, indicative of its non-inhibited degradation even at influent concentration of 30.8 mg L^− 1. The subMBR was operated at almost stable and constant flux of 0.22 m³ m^− 2 d^− 1 at a mean HRT of 13.6 h.     

On the performances of lead dioxide and boron-doped diamond electrodes in the anodic oxidation of simulated wastewater containing the Reactive Orange 16 dye

The performances of the Ti-Pt/β-PbO₂ and boron-doped diamond (BDD) electrodes in the electrooxidation of simulated wastewaters containing 85 mg L⁻¹ of the Reactive Orange 16 dye were investigated using a filter-press reactor. The electrolyses were carried out at the flow rate of 7 L min⁻¹, at different current densities (10-70 mA cm⁻²), and in the absence or presence of chloride ions (10-70 mM NaCl). In the absence of NaCl, total decolourisation of the simulated dye wastewater was attained independently of the electrode used. However, the performance of the BDD electrode was better than that of the Ti-Pt/β-PbO₂ electrode; the total decolourisations were achieved by applying only 1.0 A h L⁻¹ and 2.0 A h L⁻¹, respectively. In the presence of NaCl, with the electrogeneration of active chlorine, the times needed for total colour removal were markedly decreased; the addition of 50 mM Cl⁻ or 35 mM Cl⁻ (for Ti-Pt/β-PbO₂ or BDD, respectively) to the supporting electrolyte led to a 90% decrease of these times (at 50 mA cm⁻²). On the other hand, total mineralization of the dye in the presence of NaCl was attained only when using the BDD electrode (for 1.0 A h L⁻¹); for the Ti-Pt/β-PbO₂ electrode, a maximum mineralization of 85% was attained (for 2.0 A h L⁻¹). For total decolourisation of the simulated dye wastewater, the energy consumption per unit mass of dye oxidized was only 4.4 kWh kg⁻¹ or 1.9 kWh kg⁻¹ using the Ti-Pt/β-PbO₂ or BDD electrode, respectively. Clearly the BDD electrode proved to be the best anode for the electrooxidative degradation of the dye, either in the presence or absence of chloride ions.     

Adsorption characteristics of sericite for cesium ions from an aqueous solution

To efficiently remove cesium ions from aqueous solution, sericite was used as a novel adsorbent. The silanol (SiO₂) and aluminol (Al₂O₃) groups in sericite are likely to play an important role in adsorption process. The maximum adsorption capacity (q_m) and adsorption constant (K_L) for cesium ions obtained from the Langmuir isotherm model were 6.68 mg/g and 0.227 L/mg, respectively and regression curve fit well with the experimental data as the 0.965 of correlation coefficients (r²). However, when the Freundlich isotherm model was used correlation coefficient (r²) was 0.973. Therefore, it was concluded that Freundlich model fits equilibrium data better than Langmuir model. When the 6.0 g/L of sericie concentration was added to aqueous solution, cesium ions were removed by about 80% and the increase was not happened above 6.0 g/L of sericite concentration any more. The process was determined as exothermic reaction because the removal efficiency of cesium ions decreased as temperature increased. Furthermore, all adsorption was completed in 120 min and comparing the pseudo first and second-order kinetic models indicates that the adsorption of cesium ions using sericite follows well the pseudo-second-order kinetics.     

Factorial experimental design for biosorption of iron and zinc using Typha domingensis phytomass

Typha domingensis phytomass was used as a biosorbent for metal ions removal from wastewater. A full 2³ factorial design of experiments was used to obtain the best conditions of biosorption of Fe³⁺ and Zn²⁺ from water solutions. The three factors considered were temperature, pH, and biosorbent dosage. Two levels for each factor were used; pH (2.5 and 6.0), temperature (25 and 45 °C), and phytomass loading weight (0.5 and 1 g/50 ml). Batch experiments were carried out using 50 ml solutions containing 10 mg/l Fe³⁺ and 4 mg/l Zn²⁺ simulating the concentration of those metals in a real wastewater effluent. The removal percentages of iron and zinc after 120 min of contact time were then evaluated. The results were analyzed statistically using the Minitab 15 statistical software to determine the most important factors affecting the metals removal efficiency. The pH was found to be the most significant factor for the two studied metal ions.     

Adsorption behavior of fluoride ions using a titanium hydroxide-derived adsorbent

The removal behavior of fluoride ions was examined in aqueous sodium fluoride solutions using a titanium hydroxide-derived adsorbent. The adsorbent was prepared from titanium oxysulfate (TiOSO₄·xH₂O) solution, and was characterized by X-ray diffraction, scanning electron microscopy, thermogravimetry-differential thermal analysis, Fourier transform infrared spectrum and specific surface area. Batchwise adsorption test of prepared adsorbent was carried out in aqueous sodium fluoride solutions and real wastewater containing fluoride ion. The absorbent was the amorphous material, which had different morphology to the raw material, titanium oxysulfate, and the specific surface area of the adsorbent (96.8 m²/g) was 200 times higher than that of raw material (0.5 m²/g). Adsorption of fluoride on the adsorbent was saturated within 30 min in the solution with 200 mg/L of fluoride ions, together with increasing pH of the solution, due to ion exchange between fluoride ions in the solution and hydroxide ions in the adsorbent. Fluoride ions were adsorbed even in at a low fluoride concentration of 5 mg/L; and were selectively adsorbed in the solution containing a high concentration of chloride, nitrate and sulfate ions. The adsorbent can remove fluoride below permitted level (< 0.8 mg/L) from real wastewaters containing various substances. The maximum adsorption of fluoride on the adsorbent could be obtained in the solution at about pH 3. After fluoride adsorption, fluoride ions were easily desorbed using a high pH solution, completely regenerating for further removal process at acidic pH. The capacity for fluoride ion adsorption was almost unchanged three times after repeat adsorption and desorption. The equilibrium adsorption capacity of the adsorbent used for fluoride ion at pH 3 was measured, extrapolated using Langmuir and Freundlich isotherm models, and experimental data are found to fit Freundlich than Langmuir. The prepared adsorbent is expected to be a new inorganic ion exchanger for the removal and recovery of fluoride ions from wastewater.     

Asymmetric TiO2 hybrid photocatalytic ceramic membrane with porosity gradient: Effect of structure directing agent on the resulting membranes architecture and performances

Asymmetric TiO₂ hybrid photocatalytic ceramic membranes with porosity gradient have been fabricated via acid-catalyzed sol–gel method. Different structure directing agents (SDAs) i.e. Pluronic P-123, Triton X-100, Tween 20 and Tween 80 were incorporated in the preparation of TiO₂ sol to obtain a porous multilayered TiO₂ coated on the alumina ceramic support. Six different SDA-modified membrane specimens were fabricated. Four of which were coated with the TiO₂ sols prepared using only one type of SDA. The remaining two specimens were fabricated via multilayer coating of different TiO₂ sols prepared using different types of SDAs. Physico-chemical and morphological properties of different TiO₂ layers were thoroughly investigated. The membrane M1 which had the most porous TiO₂ sub-layers showed a high pure water permeability of 155 L m⁻² h⁻¹ bar⁻¹. The membrane showed a relatively high Rhodamine B (RhB) removal of 2997 mg m⁻² over 8 h treatment duration in the batch photoreactor, second only to the Pluronic-based TiO₂ membrane (specific RhB removal of 3050 mg m⁻²). All membrane specimens exhibited good performances while operated in the flow-through photocatalytic membrane reactor. Over 91% of RhB removal capability was retained after 4 treatment cycles. All membranes also showed self-cleaning property by retaining >90% of initial flux after 4 treatment cycles. The flexibility of optimizing membrane performances by fine-tuning the porosity gradient configuration of the photocatalytic layer has also been demonstrated.     

Treatment of olive mill wastewater by the combination of ultrafiltration and bipolar electrochemical reactor processes

The main purpose of this study was to investigate the removal of the chemical oxygen demand (COD) from olive mill wastewater (OMW) by the combination of ultrafiltration with electrocoagulation process. Ultrafiltration process equipped with CERAVER membrane was used as pre-treatment for electrochemical process. The obtained permeate from the ultrafiltration process allowed COD removal efficiency of about 96% from OMW. Obtained permeate with an average COD of about 1.1 g dm⁻³ was treated by electrochemical reactor equipped with a reactor with bipolar iron plate electrodes. The effect of the experimental parameters such as current density, pH, surface electrode/reactor volume ratio and NaCl concentration on COD removal was assessed. The results showed that the optimum COD removal rate was obtained at a current density of 93.3 A m⁻² and pH ranging from 4.5 to 6.5. At the optimum operational parameters for the experiments, electrocoagulation process could reduce COD from 1.1 g dm⁻³ to 78 mg dm⁻³, allowing direct discharge of the treated OMW as that meets the Algerian wastewater discharge standards (<125 mg dm⁻³).     

Feasibility studies of discontinuous electro-regeneration processes in environmentally-friendly plating for chromate separation from a binary system

Project work was carried out for feasibility and possible design of semi-industrial electro-regeneration units for diluted waters typical for rinse water systems in electroplating industry. Firstly, one subject of interest was the removal of CrO₄²⁻ ions in the concentration range between 0.06 mol m⁻³ and 2.3 mol m⁻³. Ion exchange capacity of several resins under room temperature conditions was tested. A 2-compartment cell with diaphragm was found to be a suitable construction for electrochemical resin regeneration after previous discontinuous loading. The determination of resin conductivities and transport numbers was also part of the studies. Results showed sufficient high current efficiencies up to 70%. Nevertheless, low ion mobility in the resin may limit the removal rate for continuous electrodeionization. In this case, stepwise operation mode in loading and regenerating the resin bed is the only solution. Energy consumption can be lowered by using catholytes of previous electro-regeneration steps. Specific energy consumption until 0.3 kWh per treated cubic meter is to be expected.     

Copper recovery and simultaneous COD removal from copper phthalocyanine dye effluent using bipolar disc reactor

Electrochemical treatment of real acidic effluent of copper phthalocyanine dye manufacturing plant with a view to explore the feasibility of the simultaneous removal of copper and phthalocyanine using a bipolar disc electrochemical reactor has been investigated. Experiments were conducted in a bipolar capillary gap disc stack electrochemical reactor under batch recirculation mode. Electrodes were RuO₂ and IrO₂ coated on titanium as anode and titanium as cathode. Effects of current density, electrolysis time and effluent flow rate on copper recovery and simultaneous COD removal and energy consumption were critically examined. The current density of 2.5 A dm⁻² and flow rate of 20 L h⁻¹ achieved 91.1% COD removal and 90.1% copper recovery with the energy consumption of 50.86 kWh kg⁻¹ for COD removal and simultaneous recovery of copper in a bipolar disc stack reactor.     

The use of exhausted olive cake ash (EOCA) as a low cost adsorbent for the removal of toxic metal ions from aqueous solutions

The removal characteristics of cadmium (Cd(II)) and nickel (Ni(II)) ions from aqueous solution by exhausted olive cake ash (EOCA) were investigated under various conditions of contact time, pH, initial metal concentration and temperature. Batch kinetic studies showed that an equilibrium time of 2 h was required for the adsorption of Ni(II) and Cd(II) onto EOCA. Equilibrium adsorption is affected by the initial pH (pH₀) of the solution. The pH₀ 6.0 is found to be the optimum for the individual removal of Cd(II) and Ni(II) ions by EOCA. The adsorption test of applying EOCA into synthetic wastewater revealed that the adsorption data of this material for nickel and cadmium ions were better fitted to the Langmuir isotherm since the correlation coefficients for the Langmuir isotherm were higher than that for the Freundlich isotherm. The estimated maximum capacities of nickel and cadmium ions adsorbed by EOCA were 8.38 and 7.32 mg g⁻¹, respectively. The thermodynamic parameters for the adsorption process data were evaluated using Langmuir isotherm. The free energy change (ΔG°) and the enthalpy change (ΔH°) showed that the process was feasible and endothermic respectively. As the exhausted olive cake is discarded as waste from olive processing, the adsorbent derived from this material is expected to be an economical product for metal ion remediation from water and wastewater.     

CO tolerance effects of tungsten-based PEMFC anodes

The performance of proton exchange membrane fuel cells (PEMFC) fed with CO-contaminated hydrogen was investigated for anodes with PtWO_x/C and phosphotungstic acid (PTA) impregnated Pt/C electrocatalysts. A quite high performance was achieved for the PEMFC fed with H₂ + 100 ppm CO with anodes containing 0.4 mg PtWO_x cm⁻² and also for those with 0.4 mg Pt cm⁻² impregnated with ca. 1 mg PTA cm⁻². A decay of the single cell performance with time is observed, and this was attributed to an increase of the membrane resistance due to the polymer degradation promoted by the crossover of the tungsten species throughout the membrane.     

Effect of ionic strength on the foam fractionation of BSA with existence of antifoaming agent

Foam fractionation is an economical and effective technology for protein concentration and separation. However, the presence of antifoaming agent in the fermentation broth restricts the application of this technology. In this paper surfactant-assisted foam process was conducted with a mimic system using bovine serum albumin (BSA) as target protein, polyoxypropylene polyoxyethylene glylerin ether (PGE) as antifoaming agent and cetyltrimethyl ammonium bromide (CTAB) as surfactant, putting emphasis on study of the effect of ionic strength on the separation process. The experimental results showed that with ionic strength increasing, the mixed-system foaming ability gradually increased. Under the conditions of C_BSA 100 mg/L, C_CTAB 20 mg/L, C_PGE 8 mg/L and pH 7.4, feed liquid 250 mL, air flow rate 100 mL/min at 25 °C, the maximum enrichment ratio of BSA reached 27 when the ionic strength was 0.0500 mol/kg and the maximum recovery of BSA reached 80.5% when the ionic strength was 0.1696 mol/kg. Furthermore, K⁺ had better separate efficiency than Na⁺ under the same ionic strength.     

Optimization of process parameters for electrochemical nitrate removal using Box-Behnken design

Electrochemical reduction of nitrate in an undivided cell was studied in the present experiments. The optimization of the influencing factors on electrochemical reduction of nitrate by response surface methodology (RSM) was also studied. An ideal condition of performing both cathodic reduction of nitrate and anodic oxidation of the formed by-product in the presence of NaCl was achieved in the present experiment. The Box-Behnken design can be employed to develop mathematical models for predicting electrochemical nitrate removal geometry. The removal is sensitive to the current density and time in the present study. The value of R² > 0.99 for the present mathematical model indicates the high correlation between observed and predicted values. The optimal NaCl dosage, current density and electrolysis time for nitrate removal in the present experiment are 0.47 g L⁻¹, 26.06 mA cm⁻², and 111.88 min, respectively, at which the nitrate nitrogen (nitrate-N) and ammonia nitrogen (ammonia-N) concentration in the treated solution are 9.80 and 0 mg L⁻¹, respectively, which will meet the standards for drinking water.