Detoxification of hexavalent chromium in wastewater containing organic substances using simonkolleite-TiO2 photocatalyst

Innovative simple method for the preparation of simonkolleite-TiO₂ photocatalyst with different Zn contents was achieved. The prepared photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, Raman and diffuse reflectance spectroscopy techniques. The photocatalytic activities of the materials were evaluated for the simultaneous detoxification of hexavalent chromium (Cr(VI)) and oxidation of organic compounds commonly present in wastewater under simulated solar light. The best photoreduction efficiency of Cr(VI) has been achieved at 1000 ppm simonkolleite-TiO₂ photocatalyst of 5% Zn/TiO₂ weight ratio, and pH value of 2.5 to enhance the adsorption onto catalyst surface. Photoreduction was significantly improved by using formic acid as holes scavenger owing to its chemical adsorption on the catalyst surface. Finally, 100% photoreduction of Cr(VI) could be achieved using formic/simonkolleite-TiO₂ systems under sunlight.     

Biosorption of Co(II) ions from aqueous solution using Chrysanthemum indicum: Kinetics,equilibrium and thermodynamics

The present study investigates the adsorption potential of Chrysanthemum indicum flower in its raw (CIF-R) and biochar (CIF-BC) form for the removal of cobalt ions from aqueous solution. The adsorbents were characterized for their surface area using BET analysis, surface morphology and elemental composition with SEM-EDAX and for the presence of functional groups by FTIR analysis. Batch adsorption experiments were carried out to evaluate the effect of process parameters, viz. pH, adsorbent dosage, initial metal ion concentration, contact time, stirring speed, presence of interfering ions and temperature on the adsorption of Co(II) ion using both the adsorbents. The optimum conditions for maximum removal of Co(II) ion was ascertained to be pH 5 for both adsorbents, adsorbent dose of 4 g/L and 3 g/L, equilibrium time of 60 min and 45 min, respectively, for CIF-R and CIF-BC. The maximum adsorption capacity of CIF-R and CIF-BC was found to be 14.84 mg/g and 45.44 mg/g, respectively, for the removal of Co(II) ion. The mechanism of adsorption was studied using different models of adsorption kinetics, isotherms and thermodynamics. It was inferred that Co(II) adsorption on both CIF-R and CIF-BC followed pseudo-second order kinetics and Langmuir isotherm model with the process being spontaneous and endothermic in nature.     

Adsorptive removal of basic dyes from aqueous solutions by surfactant modified bentonite clay (organoclay): Kinetic and competitive adsorption isotherm

Cationic surfactant (Hexadecyltrimenthylammonium chloride) modified bentonite clay was prepared and systematically studied for its adsorption behavior as an efficient adsorbent for the removal of basic dyes such as methylene blue (MB), crystal violet (CV) and Rhodamine B (RB) from aqueous phase. Organo modified clay shows better capacity for the removal of three dyes. The adsorption process was found to be dependent on pH and initial dye concentration. The maximum dye sorption was found to be at a pH of 9.0 (99.99% for MB, 95.0% for CV and 83.0% for RB). The adsorption capacity for the dyes was found to be 399.74, 365.11 and 324.36 μmol/g for MB, CV and RB, respectively at 30 °C. The equilibrium uptake was attained within 240 min. The kinetic studies were revealed that sorption follows a pseudo-second-order kinetic model which indicates chemisorption between adsorbent and adsorbate molecules. Adsorption isotherm indicates non-energetically adsorption sites which fit with Freundlich isotherm model. The fitness of kinetics and isotherm models was evaluated by using HYBRID error analysis function. Competitive adsorptions of dyes were studied by using binary component systems.     

Synthesis of hydroxyapatite/clay and hydroxyapatite/pumice composites for tetracycline removal from aqueous solutions

Synthesized hydroxyapatite/clay (HA-C) and hydroxyapatite/pumice (HA-P) composites were used for tetracycline (TC) uptake studies from aqueous solution and their uptake capacities were compared. HA-C and HA-P composites were synthesized by precipitation method and the structures of the synthesized composites were characterized by XRD, SEM and BET analyses. Cation exchange capacities of HA-C and HA-P were found to be 84 meq/100 g and 33 meq/100 g, respectively. The TC adsorption using HA-C and HA-P was studied on batch mode. Various parameters such as contact time, solution pH, initial TC concentration, composite dosage, salinity and temperature were optimized. Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models were applied to the equilibrium data. The maximum adsorption capacity onto HA-C was found to be 76.02 mg/g and about four times larger than the adsorption capacity of the HA-P (17.87 mg/g). The results indicated that the TC uptake onto HA-C and HA-P composites is mainly by a surface complexation and ion-exchange mechanism which depend on the solution pH. The calculated values of thermodynamic parameters indicated that the TC adsorption is favorable, physicochemical in nature. The sorption process follows pseudo-second-order and intraparticle diffusion kinetic models. The TC adsorption mechanism by HA-C and HA-P has been proposed.     

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.     

Isotherm and kinetic studies for the biosorption of cadmium from aqueous solution by Alhaji maurorum seed

Cadmium is an extremely toxic metal commonly found in industrial regions. Anthropogenic activity is the most important factor causing its interference to water, soil and air resources. The aim of many researches is to present remediation strategy or to remove cadmium from contaminated resources through an economical and efficient method. Cadmium adsorption from aqueous solution using Alhaji maurorum seed adsorbent has been investigated and optimized in this study. Moreover, isotherm and kinetics of adsorption process was studied. The seeds are washed by distilled water after separation from the plant, and then dried in room temperature for 48 h. They are powdered by grinder and passed through sieve no.18 as well. Adsorption process was optimized in 4 steps regarding pH, contact time, adsorption dose and initial concentration of cadmium effects. The cadmium concentration in solution was measured using ICP-OES method. The results of optimization tests showed that the optimum condition of cadmium adsorption (85.5% removal) occurs at pH of 6.5 with 20 g/L of adsorption dose for 45 min. In addition, the efficiency of adsorption process increases as the cadmium concentration reduces in the initial solution. Adsorption process follows the pseudo second-order kinetics and Freundlich isotherm with correlation coefficients of 0.999 and 0.99, respectively. According to the findings of this analysis, it was concluded that A. maurorum seed is a good biological adsorbent for adsorbing cadmium from aqueous solution.     

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.     

Evaluation of Abelmoschus esculentus (lady's finger) seed as a novel biosorbent for the removal of Acid Blue 113 dye from aqueous solutions

The use of a new biosorbent derived from Abelmoschus esculentus (A. esculentus) seed for the removal of Acid Blue 113 (AB113) in aqueous solutions was investigated in batch mode. Biosorption studies were carried out under varying operational parameters including initial pH, biosorbent dosage, contact time, initial dye concentration and temperature. The results indicated that the biosorption properties were strongly dependent on initial pH. Fourier transform infrared spectroscopy analysis revealed that hydroxyl, carboxylic and amide functional groups present on the biosorbent surface were involved in the dye removal process. Equilibrium data were best fitted by the Langmuir model. The maximum biosorption capacity was 169.9 ± 3.1 mg g⁻¹ at 25 °C and initial pH 5.5. The kinetic data were in good agreement with the pseudo-second-order kinetic model. The process was controlled by diffusion through boundary layer at the initial stage followed by intra-particle diffusion at the later stage. Thermodynamic evaluation showed that the process was endothermic and spontaneous. The present study suggests that A. esculentus seed with maximum biosorption capacity which compared well with values reported in the literature can be a potential biosorbent for AB113 dye removal.     

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.     

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.     

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.     

Synthesis and adsorption studies of NiO nanoparticles in the presence of H2acacen ligand,for removing Rhodamine B in wastewater treatment

Cost efficient NiO nanoparticles were synthesized by hydrothermal production of nano-scale Ni(OH)₂, using Ni(NO₃)₂·6H₂O and NaOH as precursors, in the presence of H₂acacen ligand, followed by calcinations of the produced Ni(OH)₂. Prepared samples were then characterized using X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), Fourier transform infrared (FT-IR) spectra, Brunauer–Emmet–Teller (BET) and transmission electron microscopy (TEM). BET analysis revealed high surface area for pure nano sized NiO, averaging 176.56 m²/g and confirming its application as an efficient adsorbent. Experimental studies for Rhodamine B (RB) removal from aqueous solutions in batch systems revealed that the adsorption equilibrium was best represented by Langmuir isotherm, with the maximum monolayer capacity of 111 mg/g for RB. The kinetic data was well described by a pseudo-second-order kinetic model, having intraparticle diffusion model as a rate limiting step.     

Boron removal from produced water using electrocoagulation

Produced water is the largest wastestream of oil and gas exploration but its chemical composition hinders its beneficial use. Effective treatment and reuse of produced water can mitigate scarcity of fresh water, especially in arid areas. Presence of inorganic compounds such as boron in produced water renders its beneficial use difficult. In this study, boron removal from produced water was investigated. Synthetic wastewater was prepared simulating the range of boron concentrations in produced water. Four operating parameters pH (3–11), charge loading (1200–3600 Ah/m³), contact time (15–90 min) and concentration (10–30 mg/L) were selected and their optimum conditions investigated. The obtained optimum conditions were applied to treat real produced water. Residual boron concentration of 0.3 mg/L was obtained from initial boron concentration of 15 mg/L in real produced water at optimum conditions of pH 7, charge loading 2400 Ah/m³ and contact time 90 min. Boron adsorption could be represented by Langmuir and Freundlich isotherm models. Electrocoagulation can be used for the effective removal of boron from produced water.     

Development and physicochemical characterization of a new magnetic nanocomposite as an economic antibiotic remover

Maghemite (ϒ-Fe₂O₃) nanoparticles were impregnated to nanoporous carbon obtained from tomato waste (TWNC). The prepared magnetic composite (MTWNC) was characterized and used to remove tetracycline (TC) from water and then easily be separated from the medium by a magnetic technique. The morphologies and surface chemistries of both magnetic and non-magnetic nanoporous carbons were studied by FTIR, XRD, SEM, SEM-EDX, VSM, BET surface area, proximate and elemental analysis determinations. Batch adsorption studies were carried out and the effects of pH, initial TC concentration, adsorbent dose, ionic strength and temperature were investigated. The adsorption kinetics of TC on MTWNC could be expressed well by the pseudo-second order model, and sorption isotherms were described by Langmuir equation with maximum adsorption capacity of 60.60 mg/g at pH 4 and 50 °C. Thermodynamic parameters showed that the adsorption of TC onto MTWNC was feasible, spontaneous and endothermic. Furthermore, the recyclability of the adsorbent was tested with 0.01 M NaOH solution, and the results show that the synthesized composite adsorbent could be employed repeatedly in wastewater treatment.     

Removal of a cationic bisbiguanide using Functionalized Activated Carbons (FACs)

Functionalized Granular Activated Carbons (FACs) are used as adsorbents for treating pharmaceutical wastewaters containing Chlorhexidine Gluconate. Chemical modifications of Granular Activated Carbons (GACs) using functionalizing agents like HCl and HF produce FACs. The adsorption capacity of each of FAC-HCl and FAC-HF is found to be higher than GAC. The modelled maximum adsorption capacity for FAC-HCl is 1.02 g/g of adsorbent, 3.49 g/g of adsorbent for FAC-HF and 0.0682 g/g of adsorbent for GAC. This is mainly due to the additional chemisorptions by surface complexation at the functionalized surface sites of the modified GACs. This is also supported by the well-known pseudo-second-order kinetic model. Formation of surface complexes with the functional groups and weakly polar Chlorhexidine Gluconate is well supported by the physical characterization using Energy dispersive X-ray spectroscopy (EDAX), Brunner–Emmett–Teller (BET) test and Fourier Transform Infrared spectroscopy (FTIR) analysis after adsorption. The adsorption capacity of GAC and the FACs increases in the order of FAC-HF > FAC-HCl > GAC conforming to the proportion of the total acidity of the carbon surfaces. Intra-particle diffusion is not the sole rate-controlling factor. An agreement to pseudo-second-order kinetic model, Elovich kinetic model and Boyd's film diffusion model proves that chemisorption is the rate-controlling parameter in this adsorption study.     

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.     

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.     

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.     

Comparison studies of adsorption properties of MgO nanoparticles and ZnO–MgO nanocomposites for linezolid antibiotic removal from aqueous solution using response surface methodology

In this investigation, the adsorption measure of linezolid antibiotic onto MgO nanoparticles and ZnO–MgO nanocomposites were performed. The adsorbents were characterized by different techniques such as XRD, SEM, TEM and BET. The parameters influence such as the pH, adsorbent dosage and temperature was tested and evaluated by Box–Behnken Design combined with response surface methodology. Performing adsorption tests at optimal conditions set as 0.5 g L⁻¹ of adsorbent, pH 10 and 308 K make admit to obtain high adsorption turnover (123.45 and 140.28 mg g⁻¹ for MgO nanoparticles and ZnO–MgO nanocomposites, respectively). A good compromise between predicted and experimental data in this research was observed. The experimental equilibrium data fitting to Langmuir, Freundlich, Tempkin and Dubinin–Radushkevich models indicate that the Langmuir model is a best model for evaluation of adsorption behavior. Kinetic evaluation of experimental data indicated that the adsorption operations followed well pseudo-second-order models. The adsorption capacity of ZnO–MgO nanocomposites is higher than MgO nanoparticles that because of the ZnO–MgO nanocomposites have high specific surface area.