Batch and Continuous Design of a Full‐Scale Treatment Facility for Removing Dissolved Natural Organic Matter

Batch and continuous flow adsorption experiments are carried out and the design of a full‐scale facility for removing dissolved natural organic matter (DNOM) from Catalan Lakewater is demonstrated. The adsorption efficiency is proportional to the temperature and the amount of adsorbent unlike pH increase. The highest DNOM removal rate is obtained at 35 °C, pH 4, and an adsorbent amount of 0.8 g L^?1. Optimum contact time for batch studies is 60 min at equilibrium. Correlation constants (r) of Langmuir and Freundlich isotherms are 0.8905 and 0.9739, respectively. Based on the Freundlich isotherm, the highest adsorption capacity (q_max) obtained is 2.44 and 6.01 mg DNOM/g granulated activated carbon (GAC) for raw and enriched water, respectively. Consequently, the effects of adsorbent amount, bed depth, empty bed contact time, and organic loading on removal performance are investigated in the rapid small‐scale column test (RSSCT) columns. The targeted effluent concentration of 1 mg DNOM/L can easily be achieved in the columns. At the design capacity of the facility, 15 adsorption columns with dimensions of 7 m height, 4.33 m diameter, and 22 days of operation cycle are required to remove DNOM from raw water.     

Adsorption of Metal Ions onto the Chemically Modified Agricultural Waste

This paper discusses about the adsorption of metal ions such as Cu(II), Cd(II), Zn(II), and Ni(II) from aqueous solution by sulfuric acid treated cashew nut shell (STCNS). The adsorption process depends on the solution pH, adsorbent dose, contact time, initial metal ions concentration, and temperature. The adsorption kinetics was relatively fast and equilibrium was reached at 30 min. The adsorption equilibrium follows Langmuir adsorption isotherm model. The maximum adsorption capacity values of the modified cashew nut shell (CNS) for metal ions were 406.6 mg/g for Cu(II), 436.7 mg/g for Cd(II), 455.7 mg/g for Zn(II), and 456.3 mg/g for Ni(II). The thermodynamic study shows the adsorption of metal ions onto the STCNS was spontaneous and exothermic in nature. The kinetics of metal ions adsorption onto the STCNS followed a pseudo‐second‐order kinetic model. The external mass transfer controlled metal ions removal at the earlier stages and intraparticle diffusion at the later stages of adsorption. A Boyd kinetic plot confirms that the external mass transfer was the slowest step involved in the adsorption of metal ions onto the STCNS. A single‐stage batch adsorber was designed using the Langmuir adsorption isotherm equation.     

Base Treated Cogon Grass (Imperata cylindrica) as an Adsorbent for the Removal of Ni(II): Kinetic,Isothermal and Fixed‐bed Column Studies

The adsorption of Ni(II) from aqueous solutions using base treated cogon grass or Imperata cylindrica (NHIC) was performed under batch and column modes. Batch experiments were conducted to determine the factors affecting adsorption such as pH, adsorbent dosage, initial nickel concentration, contact time and temperature. The fixed‐bed column experiment was performed to determine the practical applicability of NHIC and to obtain the breakthrough curve. Adsorption was fast as equilibrium was achieved within 60 min, and was best described by the pseudo second order model. According to the Langmuir model, a maximum adsorption capacity of 6.96 mg/g was observed at pH 5 and at a temperature of 313 K. Thermodynamic parameters such as ΔG⁰, ΔH⁰ and ΔS⁰ were calculated, and indicated that adsorption was a spontaneous and endothermic process. The mechanistic pathway of Ni(II) uptake was examined by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) spectroscopy. The Thomas and Yoon‐Nelson models were used to analyze the fixed‐bed column data.     

Investigation of Biosorption Behavior of Methylene Blue on Pleurotus ostreatus (Jacq.) P. Kumm.

The effect of varying parameters such as dye concentration, adsorbent dose, pH and temperature on the adsorption capacity of Pleurotus ostreatus is investigated. The commonly available white rot fungus Pleurotus ostreatus is investigated as a viable biomaterial for the biological treatment of synthetic basic methylene blue effluents. The results obtained from the batch experiments reveal the ability of the fungus to remove methylene blue. The performance is dependent on the dye concentration, pH, and fungal biomass. The equilibrium and kinetics of adsorption are investigated and the Langmuir equation is used to fit the equilibrium isotherm. The adsorption isotherm of methylene blue follows only the Langmuir model with a correlation coefficient of ca. 0.96–0.99. The maximum adsorption capacity is ca. 70 mg of dye per g of dry fungus at pH 11, 70 mg L^–1 dye, and 0.1 g L^–1 fungus concentration, respectively. This study demonstrates that the fungus could be used as an effective biosorbent for the treatment of dye‐containing wastewater streams.     

Modification of MCM‐41 with Anionic Surfactant: A Convenient Design for Efficient Removal of Cationic Dyes from Wastewater

The potential of MCM‐41 for the removal of cationic dyes from water solution was evaluated using sodium dodecyl sulfate (SDS) for the surface modification of this mesoporous material. Admicelle structures formed on the surface of the calcined MCM‐41 are capable of removing organic pollutants and cationic species from water environment. The structural, textural, and surface chemical characteristics of the prepared SDS‐modified MCM‐41 (SDS‐MCM‐41) were studied. The adsorption capacity of SDS‐MCM‐41 was evaluated for methylene blue (MB) as a target cationic dye. Equilibrium adsorption isotherm data were manipulated employing nonlinear regression analysis. The Langmuir, Freundlich, and Sips isotherm models were examined. The adsorption data were well fitted to both Langmuir and Sips isotherm models. The maximum adsorption capacity of SDS‐MCM‐41 for MB, based on Langmuir and Sips models, were 290.8 and 297.3 mg g^?1, respectively. Ethanol was found to be an effective solvent for partial regeneration of the adsorbent.     

Preparation,Characterization and Adsorption Mechanism of Cu(II) onto Protonated Rubber Leaf Powder

The adsorption of Cu(II) onto HCl treated rubber leaf powder (HHBL) was investigated in batch and column studies. The adsorbent was characterized by spectroscopic and quantitative analyses in order to understand the mechanism of copper adsorption. HHBL is mesoporous in nature as indicated by Bruneuer, Emmett and Teller (BET) analysis, and has various kinds of functional groups such as Si‐OH, ROH, RCOOH, RCOO^–, RNH₂, C‐O‐C and aromatic rings as detected by Fourier transform infrared (FTIR) spectroscopy. Copper adsorption was confirmed by scanning electron microscopy (SEM) and energy dispersive X‐ray spectroscopy (EDS). The equilibrium process was described well by the Langmuir isotherm model, and a maximum adsorption capacity of 8.39 mg/g was recorded for the smallest adsorbent size (<180 μm). The two main adsorption mechanisms involved were ion exchange and complexation. The fixed bed column study demonstrated satisfactory applicability of HHBL in removing Cu(II) from aqueous solutions.     

Adsorption Kinetic and Equilibrium Studies on Removal of Lead(II) onto Glutamic Acid/Sepiolite

In this study, a modified method was used to increase the adsorption of lead ions from aqueous solutions by using modified clay mineral on the laboratory scale. Adsorption experiments have been carried out on the use of both thermal activated sepiolite (TAS) and their glutamate/sepiolite modification (GS) as adsorbents. The experimental data was analyzed using adsorption kinetic models (pseudo first‐ and second‐order equations). The pseudo second‐order kinetic model fitted well to the kinetic data (R² ≥ 0.99). Then, the Freundlich and Langmuir models were applied to describe the uptake of Pb(II) on GS and the Langmuir isotherm model agrees well with the equilibrium experimental data (R² ≥ 0.97). The maximum adsorption capacity was observed to be 128.205 mg/g by GS according to the Langmuir equation. Desorption efficiency of the GS was studied by the batch method using EDTA, HCl, and HNO₃ solutions. Desorption of 69.18, 74.55, and 80% of Pb(II) from GS was achieved with 0.1 M EDTA, 0.1 M HCl, and 0.1 M HNO₃ solutions, respectively. FTIR analysis suggests the importance of functional groups such as amino, hydroxyl, and carboxyl during Pb(II) removal. SEM observations demonstrated that an important interaction at the lead‐modified sepiolite interface occurred during the adsorption process. In addition, the thermodynamic constants was calculated that the values of the Gibbs free energy (ΔG*), enthalpy (ΔH*), and entropy (ΔS*) of modification were 86.79 kJ/mol, ?18.91 kJ/mol, and ?354.70 J/mol/K, respectively. The negative value of ΔH* shows exothermic nature of adsorption.     

Adsorption behaviour of dibutyl phthalate on marine sediments

Laboratory experiments were carried out to investigate the adsorption behaviour of dibutyl phthalate (DBP) on marine sediments collected from five different sites in Victoria Harbour, Hong Kong. DBP adsorption can be well described by the Langmuir isotherm. The maximum DBP adsorption capacity (Q(max)) of the marine sediments ranges from 53 to 79 mg g(-1), which has a positive correlation with their organic content. Around 90% of the organic can be removed from the sediments with treatment by H(2)O(2) oxidation, and the Q(max) then decreases to a range between 13 and 22 mg g(-1). The black carbon content of the sediments has a much greater DBP adsorption capacity than does the natural organic matter of the sediments. The amount of DBP adsorbed on the sediments increases as the salinity of the marine water increases.     

Removal of Copper,Nickel, and Zinc Ions from Electroplating Rinse Water

Removal of copper, nickel, and zinc ions from synthetic electroplating rinse water was investigated using cationic exchange resin (Ceralite IR 120). Batch ion exchange studies were carried out to optimize the various experimental parameters (such as contact time, pH, and dosage). Influence of co‐existing cations, chelating agent EDTA on the removal of metal ion of interest was also studied. Sorption isotherm data obtained at different experimental conditions were fitted with Langmuir, Freundlich, Redlich–Peterson, and Toth models. A maximum adsorption capacity of 164 mg g^?1 for Cu(II), 109 mg g^?1 for Ni(II), and 105 mg g^?1 for Zn(II) was observed at optimum experimental conditions according to Langmuir model. The kinetic data for metal ions adsorption process follows pseudo second‐order. Presence of EDTA and co‐ions markedly alters the metal ion removal. Continuous column ion exchange experiments were also conducted. The breakeven point of the column was obtained after recovering effectively several liters of rinse water. The treated rinse water could be recycled in rinsing operations. The Thomas and Adams–Bohart models were applied to column studies and the constants were evaluated. Desorption of the adsorbed metal ions from the resin column was studied by conducting a model experiments with Cu(II) ions loaded ion exchange resin column using sulfuric acid as eluant. A novel lead oxide coated Ti substrate dimensionally stable (DSA) anode was prepared for recovery of copper ions as metal foil from regenerated liquor by electro winning at different current densities (50–300 A cm^?2).     

Adsorption of Cadmium Ions from Aqueous Solution Using Granular Activated Carbon and Activated Clay

The present study was aimed at removing cadmium ions from aqueous solution through batch studies using adsorbents, such as, granular activated carbon (GAC) and activated clay (A‐clay). GAC was of commercial grade where as the A‐clay was prepared by acid treatment of clay with 1 mol/L of H₂SO₄. Bulk densities of A‐clay and GAC were 1132 and 599 kg/m³, respectively. The surface areas were 358 m²/g for GAC and 90 m²/g for A‐clay. The adsorption studies were carried out to optimize the process parameters, such as, pH, adsorbent dosage, and contact time. The results obtained were analyzed for kinetics and adsorption isotherm studies. The pH value was optimized at pH 6 giving maximum Cd removal of 84 and 75.2% with GAC and A‐clay, respectively. The adsorbent dosage was optimized and was found to be 5 g/L for GAC and 10 g/L for A‐clay. Batch adsorption studies were carried out with initial adsorbate (Cd) concentration of 100 mg/L and adsorbent dosage of 10 g/L at pH 6. The optimum contact time was found to be 5 h for both the adsorbents. Kinetic studies showed Cd removal a pseudo second order process. The isotherm studies revealed Langmuir isotherm to better fit the data than Freundlich isotherm.     

Biosorption of Nickel from Synthetic and Electroplating Industrial Solutions using a Green Marine Algae Ulva reticulata

The present work investigated the biosorption of nickel from synthetic and electroplating industrial effluents using a green marine algae Ulva reticulata. Preliminary batch results imply that pH 4.5 was optimum for nickel uptake and the isotherm experiments conducted at this pH condition indicated that U. reticulata can biosorb 62.3 mg g^–1 nickel ions from synthetic solutions, according to the Langmuir model. Desorption was effective and practical using 0.1 M CaCl₂ (pH 2.5, HCl) and the biomass was regenerated and reused for three cycles. Continuous biosorption experiments were performed in an upflow packed column (2 cm I.D and 35 cm height). Among the two electroplating effluents used, effluent‐1 is characterized by excess co‐ions and high nickel ion content. This influenced the column nickel uptake with U. reticulata exhibiting 52.1 mg g^–1 in the case of effluent‐1 compared to 56.5 mg g^–1 in the case of synthetic solution. On the other hand U. reticulata performed well in effluent‐2 with uptakes of 53.3 and 54.3 mg g^–1 for effluent‐2 and synthetic solution, respectively. Mathematical modeling of column experimental data was performed using nonlinear forms of the Thomas‐ and modified dose‐response models, with the latter able to simulate breakthrough curves with high correlation coefficients.     

Biosorption Kinetics and Isotherm Studies of Cd(II) by Dried Enteromorpha compressa Macroalgae Cells from Aqueous Solutions

For the first time ever, Enteromorpha compressa macroalgae (ECM), which is commonly found in Turkey, has been used as biosorbent by us. This study aims to investigate the biosorption of Cd²⁺ from aqueous solutions in a batch system by using an alga of ECM in different concentrations, pH levels, agitation rates (90–150 rpm), and contact periods. The maximum biosorption capacity of the ECM was found to be 9.50 mg/g at pH 6, Cd²⁺ initial concentration of 10 mg/L and agitation rate 150 rpm. Cadmium removal efficiency was about 95%. The experimental isotherm data were analyzed using the Langmuir and Freundlich equations. Isotherm parameters for both equations were determined and discussed. The stated biosorption mechanism is explained by the Freundlich isotherm (r² = 0.998) theory. Two simplified kinetic models including a pseudo‐first‐ and second‐order equation were selected to follow the biosorption process. Kinetic parameters; rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated and discussed. It was shown that the biosorption of cadmium onto ECM could be described by the pseudo‐second‐order equation (r² > 0.99).     

Development of Polymeric and Polymer‐Based Hybrid Adsorbents for Chromium Removal from Aqueous Solution

Ferric oxide‐loaded hybrid sorbents are environmentally benign and exhibit sorption behaviors for chromium removal from waters. In the current study, glycidyl methacrylate‐based polymer (GMD) and nanosized ferric oxide loaded glycidyl methacrylate‐based polymer (GMDFe) were prepared and assayed to examine the effect of ferric oxide loading on chromium sorption from aqueous solution for the first time from the equilibrium and kinetic points of view. The experimental equilibrium data, suitably fitted by the Langmuir and Freundlich isotherms, have shown that ferric oxide loaded hybrid sorbent exhibits higher adsorption capacity than glycidyl methacrylate‐based polymer (GMD). The Langmuir isotherm model was found to be the most suitable one for the Cr(VI) adsorption. The maximum adsorption capacities of GMD and GMDFe sorbents were determined at pH 4 as 109.54 and 157.52 mg/g, respectively. A series of column experiments was carried out to determine the breakthrough curves. The column was regenerated by eluting Cr(VI) using NaOH (10% w/v) solution after adsorption studies.     

Batch and Column Experiments to Support Heavy Metals (Cu,Zn, and Mn) Transport Modeling in Alluvial Sediments Between the Mogan Lake and the Eymir Lake,Gölbaşı, Ankara

This article describes laboratory batch sorption and column transport experiments that were conducted using heterogeneous alluvial sediments with a wide physical characteristic from wells, located between Lake Mogan and Lake Eymir, Gölbaşı, Ankara. The batch sorption experiment was conducted in two separate systems, that is, single and multicomponents. Single batch experiment was performed to determine equilibrium condition between the heavy metal ions and the soil adsorption sites. The sorption isotherms data from multibatch experiments were used to calculate the sorption parameters. Single batch experiment indicated that equilibrium was attained within 9 days from the start of the sorption test. As a result of multicomponents batch experiments, for Zn and Mn, the sorption process was well described by the Freundlich or Langmuir isotherm model, whereas sorption of Cu was better described by the linear isotherm model. The K_d of Cu were found to be highest in soil 1 (32550.350 L kg⁻¹) and lowest in soil 5 (18170.76 L kg⁻¹). The maximum and minimum sorption capacity values for Zn were found to be in soil 1 (10985.148 mg kg⁻¹) and in soil 2 (8597.14 mg kg⁻¹) units, respectively. [Correction added after online publication 15 July, 2010: In the preceding sentence, the words “minimum” and “maximum” were initially switched.] Similarly, soil 1 (7587.391 mg kg⁻¹) and soil 5 (4908.695 mg kg⁻¹) units provided the maximum and minimum values for Mn. In the column experiments, flow and tracer transport was studied under saturated conditions using conservative tracer to determine the transport parameters. Transport parameter values were obtained by curve-fitting using the nonlinear least-squares optimization code CXTFIT. Results of the column experiments indicated that the dispersivity values obtained for soil samples were in the range of 0.024 to 1.13 cm.     

Biosorption of Methylene Blue from Aqueous Solution Using a Bioenergy Forest Waste: Xanthoceras sorbifolia Seed Coat

Xanthoceras sorbifolia seed coat (XSSC), a bioenergy forest waste, was used for the adsorption of methylene blue (MB) from aqueous solutions. The effects of adsorbent dosage, pH, adsorbate concentration and contact time on MB biosorption were studied. The equilibrium adsorption data was analyzed by Langmuir and Freundlich isotherm models. The results indicated that the Langmuir model provided the best correlation with the experimental data. The adsorption capacity of XSSC for MB was determined with the Langmuir model and was found to be 178.6 mg/g at 298 K. The adsorption kinetic data was modeled using the pseudo‐first order, pseudo‐second order, and intraparticle diffusion kinetic equations. It was seen that the pseudo‐second order equation could describe the adsorption kinetics, and intraparticle diffusion was not the sole rate controlling factor. Thermodynamic parameters were also evaluated. Standard Gibbs free energy was spontaneous for all interactions, and the biosorption process exhibited exothermic standard enthalpy values. The results indicated that XSSC is an attractive alternative for removing cationic dyes from wastewater.     

Metal Retention Experiments for the Design of Soil‐Mix Technology Permeable Reactive Barriers

Soil‐mix technology is effective for the construction of permeable reactive barriers (PRBs) for in situ groundwater treatment. The objective of this study was to perform initial experiments for the design of soil‐mix technology PRBs according to (i) sorption isotherm, (ii) reaction kinetics and (iii) mass balance of the contaminants. The four tested reactive systems were: (i) a granular zeolite (clinoptilolite–GZ), (ii) a granular organoclay (GO), (iii) a 1:1‐mixture GZ and model sandy clayey soil and (iv) a 1:1:1‐mixture of GZ, GO and model soil. The laboratory experiments consisted of batch tests (volume 900 mL and sorbent mass 18 g) with a multimetal solution of Pb, Cu, Zn, Cd and Ni. For the adsorption experiment, the initial concentrations ranged from 0.01 to 0.5 mM (2.5 to 30 mg/L). The maximum metal retention was measured in a batch test (300 mg/L for each metal, volume 900 mL, sorbent mass 90–4.5 g). The reactive material efficiency order was found to be GZ > GZ‐soil mix > GZ‐soil‐GO mix > GO. Langmuir isotherms modelled the adsorption, even in presence of a mixed cations solution. Adsorption was energetically favourable and spontaneous in all cases. Metals were removed according to the second order reaction kinetics; GZ and the 1:1‐mix were very similar. The maximum retention capacity was 0.1–0.2 mmol/g for Pb in the presence of clinoptilolite; for Cu, Zn, Cd and Ni, it was below 0.05 mmol/g for the four reactive systems. Mixing granular zeolite, organoclay and model soil increased the chemisorption. Providing that GZ is reactive enough for the specific conditions, GZ can be mixed to obtain the required sorption. Granular clinoptilolite addition to soil is recommended for PRBs for metal contaminated groundwater.     

Studies on the Removal of Iron from Drinking Water by Electrocoagulation – A Clean Process

The present study describes an electrocoagulation process for the removal of iron from drinking water using magnesium as the anode and galvanized iron as the cathode. Experiments were carried out as a function of pH, temperature and current density. The adsorption capacity was evaluated using both the Langmuir and the Freundlich isotherm models. The results show that the maximum removal efficiency of 98.4% was achieved at a current density of 0.06 A dm^–2, at a pH of 6.0. The adsorption of iron was better explained by fitting the Langmuir adsorption isotherm, which suggests a monolayer coverage of adsorbed molecules. The adsorption process followed a second‐order kinetics model. Temperature studies showed that adsorption was endothermic and spontaneous in nature.     

Adsorption Characteristics of Reactive Black 5 from Aqueous Solution onto Chitosan

Adsorption of reactive black 5 (RB5) from aqueous solution onto chitosan was investigated in a batch system. The effects of solution pH, initial dye concentration, and temperature were studied. Adsorption data obtained from different batch experiments were modeled using both pseudo first‐ and second‐order kinetic equations. The equilibrium adsorption data were fitted to the Freundlich, Tempkin, and Langmuir isotherms over a dye concentration range of 45–100 µmol/L. The best results were achieved with the pseudo second‐order kinetic and Langmuir isotherm equilibrium models, respectively. The equilibrium adsorption capacity (q_e) was increased with increasing the initial dye concentration and solution temperature, and decreasing solution pH. The chitosan flakes for the adsorption of the dye was regenerated efficiently through the alkaline solution and was then reused for dye removal. The activation energy (E_a) of sorption kinetics was estimated to be 13.88 kJ/mol. Thermodynamic parameters such as changes in free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) were evaluated by applying the van't Hoff equation. The thermodynamics of reactive dye adsorption by chitosan indicates its spontaneous and endothermic nature.     

Removal of Chromium from Synthetic Effluent using Nymphaea rubra

In the present work, biosorption of Cr(VI) by Nymphaea rubra was investigated in batch studies. Batch experiments were conducted to study the effect of initial sorbent dosage, solution pH and initial Cr(VI) concentration. The results showed that the equilibrium uptake capacity was increased with decrease in biomass dosage. The Cr(VI) removal was influenced by the initial chromium compound concentration. Langmuir and Freundlich adsorption isotherm models were used to represent the equilibrium data. The Freundlich isotherm model was fitted very well with the equilibrium data when compared to Langmuir isotherm model. The sorption results were analyzed for pseudo‐first order and pseudo‐second order kinetic model. It was observed that the kinetic data fitted very well with the pseudo‐second order rate equation when compared to the pseudo‐first order rate equation. Fourier transform infrared spectrum showed the presence of different functional groups in the biomass. The surface morphology of the sorbent was exemplified by SEM analysis. Aquatic weeds seem to be a promising biosorbent for the removal of chromium ions from water environment. This paper reports the research findings of a laboratory‐based study on the removal of Cr(VI) from the synthetic solution using the dried stem of N. rubra as a biosorbent.