S‐Doped Magnetic Mesoporous Carbon for Efficient Adsorption of Methyl Orange from Aqueous Solution

A simple and rapid soft‐templating coupled with one‐pot solvent thermal method is developed to synthesize S‐doped magnetic mesoporous carbon (S‐doped MMC). In this method, phenolic resin is used as a carbon precursor and Pluronic copolymer P123 is used as a template and 2,5‐dimercapto‐1,3,4‐thiadiazole is used as sulfur source. Prepared S‐doped MMC processes a high specific surface area, the Fe₃O₄ particles are well embedded in the mesoporous carbon walls that exhibit a strong magnetic response, and the hydrated iron nitrate loading amount of 0.808 g is the best. Batch adsorption experiments are carried out at different pH, initial concentration, temperature, and contact time on the adsorption of methyl orange (MO) by S‐doped MMC. The kinetic data of the adsorption process are better fitted with pseudo‐second‐order model than the pseudo‐first‐order model. Langmuir model is more suitable for the equilibrium data than Freundlich model. The thermodynamic parameters including ΔG⁰, ΔH⁰, and ΔS⁰ indicate that the adsorption is a feasible, spontaneous, and endothermic process. Finally, it is found that the coexistence of PO₄^3?, NO₃^?, SO₄^2?, Cl^?, and CO₃^2? does not influence the adsorption process. These results illustrate S‐doped MMC can be an efficient adsorbent for the removal of MO from wastewater.     

Removal of EDTA from Aqueous Solutions Using Activated Carbon Prepared from Rubber Wood Sawdust: Kinetic and Equilibrium Modeling

Adsorptive removal of EDTA (ethylenediaminetetraacetic acid) from aqueous solution was studied using steam pyrolyzed activated carbon. Rubber wood sawdust, obtained from a local timber facility at Kodangavila, Trivandrum, Kerala, India was used as the precursor for the production of the activated carbon. Batch adsorption experiments were employed to monitor and optimize the removal process. The experimental parameters, i. e., solution pH, agitation time, initial EDTA concentration and adsorbent dosage, affecting the adsorption of EDTA onto sawdust activated carbon (SDAC) were optimized. The inner core mechanism for the interaction between EDTA and SDAC, which resulted in the adsorption process, was also discussed. The change in amount of EDTA adsorbed onto SDAC and CAC (commercial activated carbon) was compared over a wide range of pH (2.0–8.0). The maximum removal of EDTA took place in the pH range of 4.0–6.0 for SDAC and 5.0–5.5 for CAC, which demonstrates the effectiveness of the former adsorbent. Kinetic as well as equilibrium studies were performed to determine the rate constant and adsorption capacity, respectively. The adsorption kinetic data was fitted with pseudo‐first‐order kinetics and the equilibrium data was shown to follow the Langmuir isotherm model. These observations explain the formation of a monolayer of EDTA on the surface of SDAC as confirmed by the slow approach to equilibrium after 4 h of contact time. The adsorption capacity of SDAC for the removal of EDTA was 0.526 mmol/g and is seen to be greater than that of CAC and other reported adsorbents (0.193–0.439 mmol/g). Finally, it is clear that the production of steam pyrolyzed activated carbon in the presence of K₂CO₃ greatly enhanced EDTA removal and resulted in a product with possible commercial value for wastewater treatment strategies.     

Studies on Adsorptive Desulfurization by Activated Carbon

Sulfur removal using adsorption requires a proper process parametric study to determine its optimal performance characteristics. In this study, response surface methodology was employed for sulfur removal from model oil (dibenzothiophene; DBT dissolved in iso‐octane) using commercial activated carbon (CAC) as an adsorbent. Experiments were carried out as per central composite design with four input parameters such as initial concentration (C₀: 100–900 mg/L), adsorbent dosage (m: 2–22 g/L), time of adsorption (t: 15–735 min), and temperature (T: 10–50°C). Regression analysis showed good fit of the experimental data to the second‐order polynomial model with coefficient of determination R²‐value of 0.9390 and Fisher F‐value of 16.5. The highest removal of sulfur by CAC was obtained with m = 20 g/L, t = 6 h, and T = 30°C.     

Adsorption of Pb(II) Ions from Aqueous Solutions by Date Bead Carbon Activated with ZnCl2

This study reports on the adsorption characteristics of Pb(II) ions from aqueous solutions using ZnCl₂‐activated date (Phoenix dactylifera) bead (ADB) carbon with respect to change in adsorbent dosage, initial pH, contact time, initial concentration, and temperature of the solution. Kinetic studies of the data showed that the adsorption follows the pseudo‐second‐order kinetic model. Thermodynamic parameters, enthalpy change (ΔH° = 55.11 kJ/mol), entropy change (ΔS° = ? 0.193 kJ/mol/K), and Gibbs free energy change (ΔG°) were also calculated for the uptake of Pb(II) ions. These parameters show that adsorption on the surface of ADB was feasible, spontaneous in nature, and endothermic between temperatures of 298.2 and 318.2 K. The equilibrium data better fitted the Langmuir and Freundlich isotherm models than the D–R adsorption isotherm model for studying the adsorption behavior of Pb(II) onto the ADB carbon. It could be observed that the maximum adsorption capacity of ADB was 76.92 mg/g at 318.2 K and pH 6.5.     

Adsorptive Removal of Acid Blue 15: Equilibrium and Kinetic Study

Activated carbons prepared from sunflower seed hull have been used as adsorbents for the removal of acid blue 15 (AB‐15) from aqueous solution. Batch adsorption techniques were performed to evaluate the influences of various experimental parameters, e. g., temperature, adsorbent dosage, pH, initial dye concentration and contact time on the adsorption process. The optimum conditions for AB‐15 removal were found to be pH = 3, adsorbent dosage = 3 g/L and equilibrium time = 4 h at 30°C. The adsorption of AB‐15 onto the adsorbent was found to increase with increasing dosage. It was found from experimental results that the Langmuir isotherm fits the data better than the Freundlich and Temkin isotherms. The maximum adsorption capacity, Q_m (at 30°C) was calculated for SF1, SF2, and SF3 as 75, 125 and 110 mg g^–1 of adsorbent, respectively. It was found that the adsorption follows pseudo‐second order kinetics. The thermodynamic parameters such as ΔG°, ΔH°, and ΔS° were also evaluated. The activated carbons prepared were characterized by FT‐IR, SEM and BET analysis.     

Selective Separation/Preconcentration of Silver Ion in Water by Multiwalled Carbon Nanotubes Microcolumn as a Sorbent

The present paper proposes the application of multiwalled carbon nanotubes (MWCNTs) as a solid adsorbent for selective separation/preconcentration of silver(I) in water samples prior to flame atomic absorption spectrometry. The procedure is based on the solid phase extraction of Ag(I)–2‐mercaptobenzothiazole chelate on MWCNTs. The elution step is carried out with 5 mL of 2 mol L^?1 HNO₃ in acetone solution at a flow rate of 1.0 mL min^?1. The influences of the various analytical parameters including pH of the solution, eluent type, sample volume, flow rates of eluent, matrix ions were investigated for optimization of the presented procedure. Tests of addition/recovery for analyte ion in real samples were performed with satisfactory results. Preconcentration factor and limit of detection for Ag(I) were 160 and 0.21 µg L^?1, respectively. The synthesized MWCNT exhibited excellent stability in eluent solution and its adsorption capacity was 5.4 mg of silver per gram of sorbent. The proposed method was successfully applied to trace silver determination in a variety of environmental water samples.     

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 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.     

Nested‐Scale Nutrient Flux in a Mixed‐Land‐Use Urbanizing Watershed

To improve quantitative understanding of mixed‐land‐use impacts on nutrient yields, a nested‐scale experimental watershed study design (n = 5) was applied in a 303(d), clean water act impaired urbanizing watershed of the lower Missouri River Basin, USA. From 2010 to 2013, water samples (n = 858 sample days per site) were analysed for total inorganic nitrogen (TIN‐N), nitrite (NO₂–N) nitrate (NO₃–N), ammonia (NH₃–N), and total phosphorus (TP‐P). Annual, seasonal, and monthly flow‐weighted concentrations (FWCs) and nutrient yields were estimated. Mean nutrient concentrations were highest where agricultural land use comprised 58% of the drainage area (NH₃ = 0.111 mg/l; NO₂ = 0.045 mg/l; NO₃ = 0.684 mg/l, TIN = 0.840 mg/l; TP = 0.127 mg/l). Average TP‐P increased by 15% with 20% increased urban land use area. Highly variable annual precipitation was observed during the study with highest nutrient yields during 2010 (record setting wet year) and lowest nutrient yields during 2012 (extreme drought year). Annual TIN‐N and TP‐P yields exceeded 10.3 and 2.04 kg ha^?1 yr^?1 from the agricultural dominated headwaters. Mean annual NH₃–N, NO₂–N, NO₃–N, TIN‐N, and TP‐P yields were 0.742, 0.400, 4.24, 5.38, and 0.979 kg ha^?1 yr^?1, respectively near the watershed outlet. Precipitation accounted for the majority of the explained variance in nutrient yields (R² values from 0.68 to 0.85). Nutrient yields were also dependent on annual precipitation of the preceding year (R² values from 0.87 to 0.91) thus enforcing the great complexity of variable mixed‐land‐use mediated source‐sink nutrient yield relationships. Study results better inform land managers and best management practices designed to mitigate nutrient pollution issues in mixed‐land‐use freshwater ecosystems. Copyright © 2015 John Wiley & Sons, Ltd.     

Sulfur and Carbon Co‐doped TiO2 Composite Fabricated by Lignosulphonate and Its Suitability for Removal of Cadmium

Highly toxic divalent cadmium causes serious environmental issues. To quickly monitor and/or efficiently remove this potentially toxic metal ion as well as to explore its interfacial chemistry with metal oxides, a sulfur and carbon co‐doped titania (S/C‐TiO₂) composite is synthesized via a facile sol‐gel method with the assistance of sodium lignosulphonate (SLS). The prepared composite displays a well‐crystallized TiO₂ nanostructure comprising the anatase phase. Both S and C, which are derived from the SLS template, are found to enter the TiO₂ lattice. The S/C‐TiO₂ composite exhibits a porous structure with a wide pore size distribution. The newly synthesized composite shows adsorption capability for the potentially toxic metal Cd(II). The adsorption process requires <5 min to reach equilibrium. The measured equilibrium adsorption capacity is 19.42 mg g^?1, which is twice as high as that of bare TiO₂. The removal efficiency is as high as 97%. Moreover, the materials are suitable for contaminated solutions over a wide range of pH values and various initial cadmium concentrations. A mechanism for the enhanced adsorption behavior is also proposed.     

Synthesis and Characterization of Poly(2‐hydroxyethylmethacrylate‐hydroxyapatite) a Novel Composite for the Removal of Lead(II) from Aqueous Solutions

In the present study, a novel adsorbent, poly (2‐hydroxyethylmethacrylate‐hydroxyapatite) [P(HEMA‐Hap)], was prepared and characterized. The synthesis was achieved by means of free‐radical polymerization and a number of structural characterization methods, including FT‐IR, XRD, TGA, SEM, BET‐porosity, and swelling tests. Pb²⁺ adsorption was performed using a series of pH, time, and temperature ranges. The reusability of the composite was also tested. The results obtained indicated that the novel adsorbent is able to bind Pb²⁺ ions with strong chemical affinity. The adsorption results were fitted to the classic Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) sorption models. Thermodynamic parameters obtained demonstrated that the sorption process was spontaneous (ΔG < 0), endothermic (ΔH > 0), as expected. The process was also consistent with the pseudo‐second‐order model, and chemical adsorption was determined to be the rate‐controlling step. It was also shown that the composite could be used for five consecutive adsorption processes.     

Metal Ion Extraction with Bipyridine Derivatives as Chelating Ligands in Supercritical Carbon Dioxide

Three fluorinated bipyridine ligands have been designed and synthesized as chelating agents for the extraction of metal ions in supercritical CO₂ (sc‐CO₂). The ligand solubilities in sc‐CO₂ were investigated at different temperatures and pressures, and the measured data have been correlated using a semiempirical model. The calculated results showed satisfactory agreement with the experimental data. Based on these data, metal ion extraction with the three compounds as chelating agents in sc‐CO₂ was performed from spiked filter paper, whereby ligand 1 showed the highest extraction efficiency, especially for Ni²⁺ and Cu²⁺. The extraction constants, K_ex, of the three chelating ligands were seen to increase with increasing extraction efficiency for the same metal ion in the same extraction system.     

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.     

The first post‐injection seismic monitor survey at the Ketzin pilot CO2 storage site: results from time‐lapse analysis

The injection of CO₂ at the Ketzin pilot CO₂ storage site started in June 2008 and ended in August 2013. During the 62 months of injection, a total amount of about 67 kt of CO₂ was injected into a saline aquifer. A third repeat three‐dimensional seismic survey, serving as the first post‐injection survey, was acquired in 2015, aiming to investigate the recent movement of the injected CO₂. Consistent with the previous two time‐lapse surveys, a predominantly west–northwest migration of the gaseous CO₂ plume in the up‐dip direction within the reservoir is inferred in this first post‐injection survey. No systematic anomalies are detected through the reservoir overburden. The extent of the CO₂ plume west of the injection site is almost identical to that found in the 2012 second repeat survey (after injection of 61 kt); however, there is a significant decrease in its size east of the injection site. Assessment of the CO₂ plume distribution suggests that the decrease in the size of the anomaly may be due to multiple factors, such as limited vertical resolution, CO₂ dissolution, and CO₂ migration into thin layers, in addition to the effects of ambient noise. Four‐dimensional seismic modelling based on dynamic flow simulations indicates that a dynamic balance between the newly injected CO₂ after the second repeat survey and the CO₂ migrating into thin layers and being dissolved was reached by the time of the first post‐injection survey. In view of the significant uncertainties in CO₂ mass estimation, both patchy and non‐patchy saturation models for the Ketzin site were taken into consideration.     

Removal of Organic Dyes in Environmental Water onto Magnetic‐Sulfonic Graphene Nanocomposite

A magnetic‐sulfonic graphene nanocomposite (G‐SO₃H/Fe₃O₄) was synthesized and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray diffraction. It was used for removal of three cationic dyes: safranine T (ST), neutral red (NR), victoria blue (VB), and three anionic dyes: methyl orange, brilliant yellow, and alizarin red, from environmental water. The experimental conditions were optimized, including pH, amount of adsorbent, adsorption kinetics, adsorption isotherms, ionic strength, etc. The results show that G‐SO₃H/Fe₃O₄ can adsorb cationic dyes more efficiently and selectively than anionic dyes at pH 6.0. In the first 10 min of adsorption time, more than 93% of the cationic dyes were removed by the sorbent. Adsorption kinetics follow the pseudo‐second‐order kinetic model well. The adsorption isotherm coincided with Langmuir and Freundlich adsorption models. The maximum adsorption capacities of G‐SO₃H/Fe₃O₄ for ST, NR, and VB dyes were 199.3, 216.8, and 200.6 mg g^?1. The adsorbed cationic dyes were eluted by using different pH values of ethanol as the solvent. The established method was simple, sensitive, and rapid, and was suitable for the adsorption of cationic dyes in environmental water.     

Treatment of Arsenic Contaminated Groundwater Using Calcium Impregnated Granular Activated Carbon in a Batch Reactor: Optimization of Process Parameters

This paper is an experimental investigation into the removal of arsenic species from simulated groundwater by adsorption onto Ca²⁺ impregnated granular activated carbon (GAC‐Ca) in the presence of impurities like Fe and Mn. The effects of adsorbent concentration, pH and temperature on the percentage removal of total arsenic (As(T)), As(III) and As(V) have been discussed. Under the experimental conditions, the optimum adsorbent concentration of GAC‐Ca was found to be 8 g/L with an agitation time of 24 h, which reduced As(T) concentration from 188 to 10 μg/L. Maximum removal of As(V) and As(III) was observed in a pH range of 7–11 and 9–11, respectively. Removal of all the above arsenic species decreased slightly with increasing temperature. The presence of Fe and Mn increased the adsorption of arsenic species. Under the experimental conditions at 30°C, the maximum percentage removals of As(T), As(III), As(V), Fe, and Mn were found to be ca. 94.3, 90.6, 98.0, 100 and 63%, respectively. It was also observed that amongst the various regenerating liquids used, a 5 N H₂SO₄ solution exhibited maximum regeneration (ca. 91%) of the spent GAC‐Ca.     

Adsorption of Cationic Dyes from Aqueous Solution by Termite Feces,a Non‐Conventional Adsorbent

The adsorption of three cationic dyes (rhodamine B, RB; crystal violet, CV; and malachite green, MG) onto termite feces, a low‐cost adsorbent, was investigated. The adsorbent was characterized by IR spectroscopy, point of zero charge measurement, and the Boehm titration method. The adsorption follows the pseudo‐second‐order kinetic model and the Langmuir–Freundlich isotherm with maximum adsorption capacities of 95.53 mg g^?1 (RB), 75.71 mg g^?1 (CV), and 44.78 mg g^?1 (MG). The study of thermodynamics showed that the adsorption is a spontaneous and endothermic process. This works suggest that termite feces can be used as a new low‐cost adsorbent for cationic dye removal.     

Adsorption of Thallium(I) Ions Using Eucalyptus Leaves Powder

Using batch method, the adsorption of thallium(I) ions from aqueous solutions on eucalyptus leaves powder, as a low cost adsorbent, was studied. The effect of various modification of considered adsorbent on the adsorption percentage of Tl(I) is an important feature of this study. The results showed that the unmodified and acidic modified adsorbent are the poor adsorbents for the Tl(I) ions while basic modified adsorbent is a suitable adsorbent. Also, the effect of some experimental conditions such as solution initial pH, agitation speed, contact time, sorbent dosage, temperature, particle size, and thallium initial concentration was studied. The results showed that the adsorption percentage depends on the conditions and the process is strongly pH‐dependent. The satisfactory adsorption percentage of Tl(I) ions, 81.5%, obtained at 25 ± 1°C. The equilibrium data agreed fairly better with Langmuir isotherm than Freundlich and Temkin models. The value of q_m that was obtained by extrapolation method is 80.65 mg g^?1. Separation factor values, R_L, showed that eucalyptus leaves powder is favorable for the sorption of Tl(I). The negative values of ΔH⁰ and ΔS⁰ showed that the Tl(I) sorption is an exothermic process and along with decrease of randomness at the solid–solution interface during sorption, respectively.     

Adsorption of Zinc using Tea Factory Waste: Kinetics,Equilibrium and Thermodynamics

In India, the annual production of tea is ca. 857,000 tonnes, which is 27.4% of the total world production. The amount of tea factory waste (TFW) produced per annum after processing is ca. 190,400 tonnes. TFW can be used as a low cost adsorbent for the removal of toxic metals from the aqueous phase. An investigation was carried out to study the feasibility of the use of TFW as an adsorbent for the removal of the heavy metal, zinc. Equilibrium, kinetic and thermodynamic studies were reported. The straight line plot of log (q_e–q) versus time t for the adsorption of zinc shows the validity of the Lagergren equation. The various steps involved in adsorbate transport from the solution to the surface of the adsorbent particles were dealt with by using a Weber‐Morris plot, q_e versus t^0.5 for the TFW. The rate controlling parameters, k_id,1 and k_id,2, were determined and it was found that the macro‐pore diffusion rate was much larger than micro‐pore diffusion rate. A batch sorption model, which assumes the pseudo‐second‐order mechanism, was used to predict the rate constant of sorption, the equilibrium sorption capacity and the initial sorption rate with the effect of initial zinc (II) ion concentration. Equilibrium data obtained from the experiments were analyzed with various isotherms, i. e., Freundlich, Langmuir, Redlich‐Peterson and Tempkin. The adsorption equilibrium was reached in 30 min and the adsorption data fitted well to all models. The maximum adsorption capacity of TFW for zinc (II) ions was determined to be 14.2 mg/g. The capacity of adsorption on Zn(II) increased with increasing temperatures and pH. The maximum uptake level of zinc was observed at pH of 4.2. The various thermodynamic parameters, i. e., ΔG°, ΔH° and ΔS°, were estimated. The thermodynamics of the zinc ion/TFW system indicated a spontaneous, endothermic and random nature of the process. The results showed that the TFW, which has low economical value, is a suitable adsorbent for the removal of zinc (II) ions from aqueous solutions.