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.     

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.     

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.     

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.     

Investigation of mercury (II) adsorption from aqueous solution onto copper oxide nanoparticles: Optimization using response surface methodology

Response surface methodology was practicable to optimize the mercury (II) removal using copper oxide nanoparticles in an aqueous matrice. The copper oxide nanoparticles structure was performed by TEM, SEM, XRD and BET. The experiment reactions were carried out based on a Box–Behnken design (BBD) and evaluated using RSM. Batch mode tests were conducted to prognosticate the adsorption equilibrium. The three parameters influence on the mercury removal was inquired by a response surface methodological approach. In study, influence of adsorbent dose, pH and temperature on the mercury removal unto copper oxide nanoparticles has been performed. The importance of the independent factors and their interactions were investigated by the ANOVA. The optimum pH, adsorbent dose and temperature were obtained to be 9.0, 0.05 g and 278 K, respectively.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Mesoporous simonkolleite–TiO2 nanostructured composite for simultaneous photocatalytic hydrogen production and dye decontamination

In the present work, mesoporous simonkolleite–TiO₂ composite was prepared with sol–gel method. The composite photocatalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), and Raman spectroscopy. Also, surface area and particle size were analyzed using BET equation. The photocatalytic hydrogen production with simultaneous decolorization of Remazole Red (F3B) dye was investigated over TiO₂ and simonkolleite–TiO₂ composite under UV–vis light irradiation. It was worthy to be noted that the rate of hydrogen production over simonkolleite–TiO₂ is higher that produced over TiO₂. The maximum amount of photocatalytic-produced hydrogen was 2.1 mmol and 3.3 mmol within 240 min using TiO₂ and simonkolleite–TiO₂ composite, respectively. The specific production rate of hydrogen from photocatalytic conversion of dye was calculated. Improvement of apparent quantum yield (22.07%) after 5 h was achieved upon addition of simonkolleite to TiO₂. This high apparent quantum yield proves that the system proposed in this study could be a hopeful approach toward using sunlight energy as outlook energy source. The obtained results suggested that a new process for H₂ production from wastewater could be achieved. The process also provides a method for degradation of organic pollutants with simultaneous H₂ production.     

Magnetophoretic separation of Chlorella sp.: Role of cationic polymer binder

Cationic polyelectrolyte promoted effective attachment of iron oxide nanoparticles (IONPs) onto microalgal cells through electrostatic attraction. Poly(diallyldimethylammonium chloride) (PDDA) and chitosan (ChiL), both are cationic polymer, are feasible to act as binding agent to promote rapid magnetophoretic separation of Chlorella sp. through low gradient magnetic separation (LGMS) with field gradient ▿B less than 80 T/m in real time. Cell separation efficiency up to 98% for the case of PDDA and 99% for the case of ChiL can be achieved in 6 min when 3 × 10⁷ cells/mL Chlorella sp. are exposed to 300 mg/L surface functionalized-IONPs (SF-IONPs). Different polyelectrolytes do not give significant effect on cell separation efficiency as long as the particle attachment occurred. However, the PDDA is more preferable as the binder for all type of microalgae medium than the chitosan (ChiL) since it is not pH dependent. SF-IONPs coated with PDDA guarantee the cell separation performance for all pH range of cell medium, with 98.21 ± 0.40% at pH 8.84. On the other hand, the ChiL performance will be affected by the cell medium pH, with only 22.93 ± 31.03% biomass recovery at pH 9.25.     

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.     

pH-conditioning for simultaneous removal of arsenic and iron ions from groundwater

The effects of some commonly used pH conditioners, viz., lime, banana ash, the carbonate and the bicarbonate of sodium and potassium and their binary mixture, on simultaneous removal of arsenic and iron ions from water have been studied. KHCO₃ has been found to be the most suitable pH conditioner for the purpose. About 80 mg/L KHCO₃ can remove both arsenate and iron ions from initial 250 μg/L and 20 mg/L to below their respective guideline values of the WHO for drinking water, retaining the final pH in the acceptable range for drinking. The simultaneous removal of arsenate and iron by the pH-conditioners decreases in the order: Lime > KHCO₃ > NaHCO₃ > K₂CO₃ > Na₂CO₃ > ash. However, lime requires post-treatment correction of highly alkaline pH. The arsenate ion is removed predominantly through goethite or ferrihydrite in the presence of the bicarbonates and through ferric hydroxide in the presence of the more alkaline pH-conditioners. KHCO₃ is more advantageous over the more basic substances including NaHCO₃, because with it, one not only needs the smallest dose but also can avoid careful adjustment of the dose for regulating the initial and the final pH. The paper clearly demonstrates the potential of KHCO₃ to substitute the currently used pH-conditioners, viz., ash, lime and NaHCO₃ for simultaneous removal of arsenate and iron ions.     

Investigation on removal of p-nitrophenol using a hybridized photo-thermal activated persulfate process: Central composite design modeling

The aim of this work is the study of p-nitrophenol (PNP) removal, as a nitroaromatic compound, using a hybridized photo-thermally activated potassium persulfate (KPS) in a fully recycled batch reactor. Response surface method was used for modeling the process. Reaction temperature, KPS initial dosage and initial pH of the solution were selected as variables, besides PNP degradation efficiency was selected as the response. ANOVA analysis reveals that a second order polynomial model with F-value of 41.7, p-value of 0.0001 and regression coefficient of 0.95 is able to predict the response. Based on the model, the process optimum conditions were introduced as initial pH of 4.5, [KPS]₀ = 1452 mg/L and T = 66 °C. Also experiments showed that using thermolysis and photolysis of the persulfate simultaneously, the role of thermolysis is not considerable. A pseudo first order kinetic model was established to describe the degradation reaction. Operational cost, as a vital industrial criterion, was estimated so that the condition of initial pH of 4.5, [KPS]₀ = 1452 mg/L and T = 25 °C showed the highest cost effective case. Under the preferred mild condition, the process will reach to 84% and 89% of degradation and mineralization efficiencies, after 60 and 120 min, respectively.     

Optimization and evaluation of an air-recirculated stripping for ammonia removal from the anaerobic digestate of pig manure

An air-recirculated stripping involved two processes and did not require any pretreatment. First, stripping CO₂ decreased the buffer capacity of the anaerobic digestate, thereby reducing the amount of lime used to achieve a high pH. Second, lime was added to increase pH and remove ammonia from the anaerobic digestate of pig manure. pH increased from 8.03 to 8.86 by stripping CO₂ in the first process (gas-to-liquid ratio = 180) and further reached 12.38 in the second process (gas-to-liquid ratio = 300). During process optimization, the maximum ammonia removal efficiency reached 96.78% with a lime dose of 22.13 g. The value was close to 98.25%, which was the optimal result predicted by response surface methodology using the software Design-Expert 8.05b. All these results indicated that air-recirculated stripping coupled with absorption was a promising technology for the removal and recovery of nitrogen in the anaerobic digestate of pig manure.