Search results for: Freundlich
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 129

Search results for: Freundlich

39 Fabrication of Electrospun Carbon Nanofibers-Reinforced Chitosan-Based Hydrogel for Environmental Applications

Authors: Badr M. Thamer

Abstract:

The use of hydrogels as adsorbents for pollutants removal from wastewater is limited due to their high swelling properties and the difficulty in recovering them after the adsorption process. To overcome these problems, a new hydrogel nanocomposite based on chitosan-g-polyacrylic acid/oxidized electrospun carbon nanofibers (CT-g-PAA/O-ECNFs) was prepared by in-situ grafting polymerization process. The prepared hydrogel nanocomposite was used as a novel effective and highly reusable adsorbent for the removal of methylene blue (MB) from polluted water with low cost. The morphology and the structure of CT-g-PAA/O-ECNFs were investigated by numerous techniques. The effect of incorporating O-ECNFs on the swelling capability of the prepared hydrogel was explored in distillated water and MB solution at normal pH. The effect of parameters including the ratio of O-ECNFs, contact time, pH, initial concentration, and temperature on the adsorption process were explored. The adsorption isotherm and kinetic were studied by numerous non-linear models. The obtained results confirmed that the incorporation of O-ECNFs into the hydrogel network improved its ability towards MB dye removal with decreasing their swelling capacity. The adsorption process depends on the pH value of the dye solution. Additionally, the adsorption and kinetic results were fitted using the Freundlich isotherm model and pseudo second order model (PSO), respectively. Moreover, the new adsorbents can be recycled for at least five cycles keeping its adsorption capacity and can be easily recovered without loss in its initial weight.

Keywords: carbon nanofibers, hydrogels, nanocomposites, water treatment

Procedia PDF Downloads 121
38 Potassium Acetate - Coconut Shell Activated Carbon for Adsorption of Benzene and Toluene: Equilibrium and Kinetic Studies

Authors: Jibril Mohammed, Usman Dadum Hamza, Abdulsalam Surajudeen, Baba Yahya Danjuma

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Considerable concerns have been raised over the presence of volatile organic compounds (VOCs) in water. In this study, coconut shell based activated carbon was produced through chemical activation with potassium acetate (PAAC) for adsorption of benzene and toluene. The porous carbons were characterized using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), proximate analysis, and ultimate analysis and nitrogen adsorption tests. Adsorption of benzene and toluene on the porous carbons were conducted at varying concentrations (50-250 mg/l). The high BET surface area of 622 m2/g and highly heteroporous adsorbent prepared gave good removal efficiencies of 79 and 82% for benzene and toluene respectively, with 32% yield. Equilibrium data were fitted to Langmuir, Freundlich and Temkin isotherms with all the models having R2 > 0.94. The equilibrium data were best represented by the Langmuir isotherm, with maximum adsorption capacity of 192 mg/g and 227 mg/g for benzene and toluene respectively. The Webber and Chakkravorti equilibrium parameter (RL) values are between 0 and 1 confirming the favourability of the Langmuir model. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The PAAC produced can be used effectively to salvage environmental pollution problems posed by VOCs through a sustainable process.

Keywords: adsorption, equilibrium and kinetics studies, potassium acetate, water treatment

Procedia PDF Downloads 190
37 Decontamination of Chromium Containing Ground Water by Adsorption Using Chemically Modified Activated Carbon Fabric

Authors: J. R. Mudakavi, K. Puttanna

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Chromium in the environment is considered as one of the most toxic elements probably next only to mercury and arsenic. It is acutely toxic, mutagenic and carcinogenic in the environment. Chromium contamination of soil and underground water due to industrial activities is a very serious problem in several parts of India covering Karnataka, Tamil Nadu, Andhra Pradesh etc. Functionally modified Activated Carbon Fabrics (ACF) offer targeted chromium removal from drinking water and industrial effluents. Activated carbon fabric is a light weight adsorbing material with high surface area and low resistance to fluid flow. We have investigated surface modification of ACF using various acids in the laboratory through batch as well as through continuous flow column experiments with a view to develop the optimum conditions for chromium removal. Among the various acids investigated, phosphoric acid modified ACF gave best results with a removal efficiency of 95% under optimum conditions. Optimum pH was around 2 – 4 with 2 hours contact time. Continuous column experiments with an effective bed contact time (EBCT) of 5 minutes indicated that breakthrough occurred after 300 bed volumes. Adsorption data followed a Freundlich isotherm pattern. Nickel adsorbs preferentially and sulphate reduces chromium adsorption by 50%. The ACF could be regenerated up to 52.3% using 3 M NaOH under optimal conditions. The process is simple, economical, energy efficient and applicable to industrial effluents and drinking water.

Keywords: activated carbon fabric, hexavalent chromium, adsorption, drinking water

Procedia PDF Downloads 294
36 Adsorption and Transformation of Lead in Coimbatore Urban Soils

Authors: K. Sivasubramanin, S. Mahimairaja, S. Pavithrapriya

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Heavy metal pollution originating from industrial wastes is becoming a serious problem in many urban environments. These heavy metals, if not properly managed, could enter into the food chain and cause a serious health hazards in animals and humans. Industrial wastes, sewage sludge, and automobile emissions also contribute to heavy metal like Pb pollution in the urban environment. However, information is scarce on the heavy metal pollution in Coimbatore urban environment. Therefore, the current study was carried out to examine the extent of lead pollution in Coimbatore urban environment the maximum Pb concentration in Coimbatore urban environment was found in ukkadam, whose concentration in soils 352 mg kg-1. In many places, the Pb concentration was found exceeded the permissible limit of 100 mg kg-1. In laboratory, closed incubation experiment showed that the concentration of different species of Pb viz., water soluble Pb(H2O-Pb), exchangeable Pb(KNO3-Pb), organic-Pb(NaOH-Pb), and organic plus metal (Fe & Al) oxides bound-Pb(Na2 EDTA-Pb) was found significantly increased during the 15 days incubation, mainly due to biotransformation processes. Both the moisture content of soil and ambient temperature exerted a profound influence on the transformation of Pb. The results of a batch experiment has shown that the sorption data was adequately described by the Freundlich equation as indicated by the high correlation coefficients (R2= 0.64) than the Langmuir equation (R2 = 0.33). A maximum of 86 mg of Pb was found adsorbed per kilogram of soil. Consistently, a soil column experiment result had shown that only a small amount of Pb( < 1.0 µg g-1 soil) alone was found leached from the soil. This might be due to greater potential of the soil towards Pb adsorption.

Keywords: lead pollution, adsorption, transformation, heavy metal pollution

Procedia PDF Downloads 302
35 Adsorption and Selective Determination Ametryne in Food Sample Using of Magnetically Separable Molecular Imprinted Polymers

Authors: Sajjad Hussain, Sabir Khan, Maria Del Pilar Taboada Sotomayor

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This work demonstrates the synthesis of magnetic molecularly imprinted polymers (MMIPs) for determination of a selected pesticide (ametryne) using high performance liquid chromatography (HPLC). Computational simulation can assist the choice of the most suitable monomer for the synthesis of polymers. The (MMIPs) were polymerized at the surface of Fe3O4@SiO2 magnetic nanoparticles (MNPs) using 2-vinylpyradine as functional monomer, ethylene-glycol-dimethacrylate (EGDMA) is a cross-linking agent and 2,2-Azobisisobutyronitrile (AIBN) used as radical initiator. Magnetic non-molecularly imprinted polymer (MNIPs) was also prepared under the same conditions without analyte. The MMIPs were characterized by scanning electron microscopy (SEM), Brunauer, Emmett and Teller (BET) and Fourier transform infrared spectroscopy (FTIR). Pseudo first order and pseudo second order model were applied to study kinetics of adsorption and it was found that adsorption process followed the pseudo first order kinetic model. Adsorption equilibrium data was fitted to Freundlich and Langmuir isotherms and the sorption equilibrium process was well described by Langmuir isotherm mode. The selectivity coefficients (α) of MMIPs for ametryne with respect to atrazine, ciprofloxacin and folic acid were 4.28, 12.32, and 14.53 respectively. The spiked recoveries ranged between 91.33 and 106.80% were obtained. The results showed high affinity and selectivity of MMIPs for pesticide ametryne in the food samples.

Keywords: molecularly imprinted polymer, pesticides, magnetic nanoparticles, adsorption

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34 Effect of Acid-Basic Treatments of Lingocellulosic Material Forest Wastes Wild Carob on Ethyl Violet Dye Adsorption

Authors: Abdallah Bouguettoucha, Derradji Chebli, Tariq Yahyaoui, Hichem Attout

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The effect of acid -basic treatment of lingocellulosic material (forest wastes wild carob) on Ethyl violet adsorption was investigated. It was found that surface chemistry plays an important role in Ethyl violet (EV) adsorption. HCl treatment produces more active acidic surface groups such as carboxylic and lactone, resulting in an increase in the adsorption of EV dye. The adsorption efficiency was higher for treated of lingocellulosic material with HCl than for treated with KOH. Maximum biosorption capacity was 170 and 130 mg/g, for treated of lingocellulosic material with HCl than for treated with KOH at pH 6 respectively. It was also found that the time to reach equilibrium takes less than 25 min for both treated materials. The adsorption of basic dye (i.e., ethyl violet or basic violet 4) was carried out by varying some process parameters, such as initial concentration, pH and temperature. The adsorption process can be well described by means of a pseudo-second-order reaction model showing that boundary layer resistance was not the rate-limiting step, as confirmed by intraparticle diffusion since the linear plot of Qt versus t^0.5 did not pass through the origin. In addition, experimental data were accurately expressed by the Sips equation if compared with the Langmuir and Freundlich isotherms. The values of ΔG° and ΔH° confirmed that the adsorption of EV on acid-basic treated forest wast wild carob was spontaneous and endothermic in nature. The positive values of ΔS° suggested an irregular increase of the randomness at the treated lingocellulosic material -solution interface during the adsorption process.

Keywords: adsorption, isotherm models, thermodynamic parameters, wild carob

Procedia PDF Downloads 246
33 Use of Magnetically Separable Molecular Imprinted Polymers for Determination of Pesticides in Food Samples

Authors: Sabir Khan, Sajjad Hussain, Ademar Wong, Maria Del Pilar Taboada Sotomayor

Abstract:

The present work aims to develop magnetic molecularly imprinted polymers (MMIPs) for determination of a selected pesticide (ametryne) using high-performance liquid chromatography (HPLC). Computational simulation can assist the choice of the most suitable monomer for the synthesis of polymers. The (MMIPs) were polymerized at the surface of Fe3O4@SiO2 magnetic nanoparticles (MNPs) using 2-vinylpyradine as functional monomer, ethylene-glycol-dimethacrylate (EGDMA) is a cross-linking agent and 2,2-Azobisisobutyronitrile (AIBN) used as radical initiator. Magnetic non-molecularly imprinted polymer (MNIPs) was also prepared under the same conditions without analyte. The MMIPs were characterized by scanning electron microscopy (SEM), Brunauer, Emmett and Teller (BET) and Fourier transform infrared spectroscopy (FTIR). Pseudo first-order and pseudo second order model were applied to study kinetics of adsorption and it was found that adsorption process followed the pseudo-first-order kinetic model. Adsorption equilibrium data was fitted to Freundlich and Langmuir isotherms and the sorption equilibrium process was well described by Langmuir isotherm mode. The selectivity coefficients (α) of MMIPs for ametryne with respect to atrazine, ciprofloxacin and folic acid were 4.28, 12.32 and 14.53 respectively. The spiked recoveries ranged between 91.33 and 106.80% were obtained. The results showed high affinity and selectivity of MMIPs for pesticide ametryne in the food samples.

Keywords: molecularly imprinted polymer, pesticides, magnetic nanoparticles, adsorption

Procedia PDF Downloads 439
32 Application of Biopolymer for Adsorption of Methylene Blue Dye from Simulated Effluent: A Green Method for Textile Industry Wastewater Treatment

Authors: Rabiya, Ramkrishna Sen

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The textile industry releases huge volume of effluent containing reactive dyes in the nearby water bodies. These effluents are significant source of water pollution since most of the dyes are toxic in nature. Moreover, it scavenges the dissolved oxygen essential to the aquatic species. Therefore, it is necessary to treat the dye effluent before it is discharged in the nearby water bodies. The present study focuses on removing the basic dye methylene blue from simulated wastewater using biopolymer. The biopolymer was partially purified from the culture of Bacillus licheniformis by ultrafiltration. Based on the elution profile of the biopolymer from ion exchange column, it was found to be a negatively charged molecule. Its net anionic nature allows the biopolymer to adsorb positively charged molecule, methylene blue. The major factors which influence the removal of dye by the biopolymer such as incubation time, pH, initial dye concentration were evaluated. The methylene blue uptake by the biopolymer is more (14.84 mg/g) near neutral pH than in acidic pH (12.05mg/g) of the water. At low pH, the lower dissociation of the dye molecule as well as the low negative charge available on the biopolymer reduces the interaction between the biopolymer and dye. The optimum incubation time for maximum removal of dye was found to be 60 min. The entire study was done with 25 mL of dye solution in 100 mL flask at 25 °C with an amount of 11g/L of biopolymer. To study the adsorption isotherm, the dye concentration was varied in the range of 25mg/L to 205mg/L. The dye uptake by the biopolymer against the equilibrium concentration was plotted. The plot indicates that the adsorption of dye by biopolymer follows the Freundlich adsorption isotherm (R-square 0.99). Hence, these studies indicate the potential use of biopolymer for the removal of basic dye from textile wastewater in an ecofriendly and sustainable way.

Keywords: biopolymer, methylene blue dye, textile industry, wastewater

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31 Removal of Metal Ions (II) Using a Synthetic Bis(2-Pyridylmethyl)Amino-Chloroacetyl Chloride- Ethylenediamine-Grafted Graphene Oxide Sheets

Authors: Laroussi Chaabane, Emmanuel Beyou, Amel El Ghali, Mohammed Hassen V. Baouab

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The functionalization of graphene oxide sheets by ethylenediamine (EDA) was accomplished followed by the grafting of bis(2-pyridylmethyl)amino group (BPED) onto the activated graphene oxide sheets in the presence of chloroacetylchloride (CAC) produced the martial [(Go-EDA-CAC)-BPED]. The physic-chemical properties of [(Go-EDA-CAC)-BPED] composites were investigated by Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPs), Scanning electron microscopy (SEM) and Thermogravimetric analysis (TGA). Moreover, [(Go-EDA-CAC)-BPED] was used for removing M(II) (where M=Cu, Ni and Co) ions from aqueous solutions using a batch process. The effect of pH, contact time and temperature were investigated. More importantly, the [(Go-EDA-CAC)-BPED] adsorbent exhibited remarkable performance in capturing heavy metal ions from water. The maximum adsorption capacity values of Cu(II), Ni(II) and Co(II) on the [(GO-EDA-CAC)-BPED] at the pH of 7 is 3.05 mmol.g⁻¹, 3.25 mmol.g⁻¹ and 3.05 mmol.g⁻¹ respectively. To examine the underlying mechanism of the adsorption process, pseudo-first, pseudo-second-order, and intraparticle diffusion models were fitted to experimental kinetic data. Results showed that the pseudo-second-order equation was appropriate to describe the three metal ions adsorption by [(Go-EDA-CAC)-BPED]. Adsorption data were further analyzed by the Langmuir, Freundlich, and Jossensadsorption approaches. Additionally, the adsorption properties of the [(Go-EDA-CAC)-BPED], their reusability (more than 10 cycles) and durability in the aqueous solutions open the path to removal of metal ions (Cu(II), Ni(II) and Co(II) from water solution. Based on the results obtained, we conclude that [(Go-EDA-CAC)-BPED] can be an effective and potential adsorbent for removing metal ions from an aqueous solution.

Keywords: graphene oxide, bis(2-pyridylmethyl)amino, adsorption kinetics, isotherms

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30 Partially Phosphorylated Polyvinyl Phosphate-PPVP Composite: Synthesis and Its Potentiality for Zr (IV) Extraction from an Acidic Medium

Authors: Khaled Alshamari

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Synthesized partially phosphorylated polyvinyl phosphate derivative (PPVP) was functionalized to extract Zirconium (IV) from Egyptian zircon sand. The specifications for the PPVP composite were approved effectively via different techniques, namely, FT-IR, XPS, BET, EDX, TGA, HNMR, C-NMR, GC-MS, XRD and ICP-OES analyses, which demonstrated a satisfactory synthesis of PPVP and zircon dissolution from Egyptian zircon sand. Factors controlling parameters, such as pH values, shaking time, initial zirconium concentration, PPVP dose, nitrate ions concentration, co-ions, temperature and eluting agents, have been optimized. At 25 ◦C, pH 0, 20 min shaking, 0.05 mol/L zirconium ions and 0.5 mol/L nitrate ions, PPVP has an exciting preservation potential of 195 mg/g, equivalent to 390 mg/L zirconium ions. From the extraction–distribution isotherm, the practical outcomes of Langmuir’s modeling are better than the Freundlich model, with a theoretical value of 196.07 mg/g, which is more in line with the experimental results of 195 mg/g. The zirconium ions adsorption onto the PPVP composite follows the pseudo-second-order kinetics with a theoretical capacity value of 204.08 mg/g. According to thermodynamic potential, the extraction process was expected to be an exothermic, spontaneous and beneficial extraction at low temperatures. The thermodynamic parameters ∆S (−0.03 kJ/mol), ∆H (−12.22 kJ/mol) and ∆G were also considered. As the temperature grows, ∆G values increase from −2.948 kJ/mol at 298 K to −1.941 kJ/mol at 338 K. Zirconium ions may be eluted from the working loaded PPVP by 0.025M HNO₃, with a 99% efficiency rate. It was found that zirconium ions revealed good separation factors towards some co-ions such as Hf⁴+ (28.82), Fe³+ (10.64), Ti⁴+ (28.82), V⁵+ (86.46) and U⁶+ (68.17). A successful alkali fusion technique with NaOH flux followed by the extraction with PPVP is used to obtain a high-purity zirconia concentrate with a zircon content of 72.77 % and a purity of 98.29%. As a result of this, the improved factors could finally be used.

Keywords: zirconium extraction, partially phosphorylated polyvinyl phosphate (PPVP), acidic medium, zircon

Procedia PDF Downloads 28
29 Comparative Study of Sorption of Cr Ions and Dye Bezaktiv Yellow HE-4G with the Use of Adsorbents Natural Mixture of Olive Stone and Date Pits from Aqueous Solution

Authors: H. Aksas, H. Babaci, K. Louhab

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In this paper, a comparative study of the adsorption of Chromium and dyes, onto mixture biosorbents, olive stones and date pits at different percentage was investigated in aqueous solution. The study of various parameters: Effect of contact time, pH, temperature and initial concentration shows that these materials possess a high affinity for the adsorption of chromium for the adsorption of dye bezaktiv yellow HE-4G. To deepen the comparative study of the adsorption of chromium and dye with the use of different blends of olive stones and date pits, the following models are studied: Langmuir, Freundlich isotherms and Dubinin- Radushkvich (D-R) were used as the adsorption equilibrium data model. Langmuir isotherm model was the most suitable for the adsorption of the dye bezaktiv HE-4G and the D-R model is most suitable for adsorption Chrome. The pseudo-first-order model, pseudo-second order and intraparticle diffusion were used to describe the adsorption kinetics. The apparent activation energy was found to be less than 8KJ/mol, which is characteristic of a controlled chemical reaction for the adsorption of two materials. t was noticed that adsorption of chromium and dye BEZAKTIV HE-YELLOW 4G follows the kinetics of the pseudo second order. The study of the effect of temperature was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy and entropy changes. The resulting thermodynamic parameters indicate the endothermic nature of the adsorption of Cr (VI) ions and the dye Bezaktiv HE-4G. But these materials are very good adsorbents, as they represent a low cost. in addition, it has been noticed that the greater the quantity of olive stone in the mixture increases, the adsorption ability of the dye or chromium increases.

Keywords: chromium ions, anions dye, sorption, mixed adsorbents, olive stone, date pits

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28 Magnetized Cellulose Nanofiber Extracted from Natural Resources for the Application of Hexavalent Chromium Removal Using the Adsorption Method

Authors: Kebede Gamo Sebehanie, Olu Emmanuel Femi, Alberto Velázquez Del Rosario, Abubeker Yimam Ali, Gudeta Jafo Muleta

Abstract:

Water pollution is one of the most serious worldwide issues today. Among water pollution, heavy metals are becoming a concern to the environment and human health due to their non-biodegradability and bioaccumulation. In this study, a magnetite-cellulose nanocomposite derived from renewable resources is employed for hexavalent chromium elimination by adsorption. Magnetite nanoparticles were synthesized directly from iron ore using solvent extraction and co-precipitation technique. Cellulose nanofiber was extracted from sugarcane bagasse using the alkaline treatment and acid hydrolysis method. Before and after the adsorption process, the MNPs-CNF composites were evaluated using X-ray diffraction (XRD), Scanning electron microscope (SEM), Fourier transform infrared (FTIR), and Vibrator sample magnetometer (VSM), and Thermogravimetric analysis (TGA). The impacts of several parameters such as pH, contact time, initial pollutant concentration, and adsorbent dose on adsorption efficiency and capacity were examined. The kinetic and isotherm adsorption of Cr (VI) was also studied. The highest removal was obtained at pH 3, and it took 80 minutes to establish adsorption equilibrium. The Langmuir and Freundlich isotherm models were used, and the experimental data fit well with the Langmuir model, which has a maximum adsorption capacity of 8.27 mg/g. The kinetic study of the adsorption process using pseudo-first-order and pseudo-second-order equations revealed that the pseudo-second-order equation was more suited for representing the adsorption kinetic data. Based on the findings, pure MNPs and MNPs-CNF nanocomposites could be used as effective adsorbents for the removal of Cr (VI) from wastewater.

Keywords: magnetite-cellulose nanocomposite, hexavalent chromium, adsorption, sugarcane bagasse

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27 Removal of Xylenol Orange and Eriochrome Black T Dyes from Aqueous Solution Using Chemically Activated Cocos nucifera and Mango Seed

Authors: Padmesh Tirunelveli Narayanapillai, Joel Sharwinkumar, Gaitri Saravanan

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The biosorption of Xylenol Orange (XO) and Eriochrome Black T (EBT) from aqueous solutions by chemically activated Cocos nucifera and mango seed as a low-cost, natural, and eco-friendly biosorbents was investigated. The study for biosorption of XO and EBT was optimized by different experimental parameters, initial pH 2–7, temperature 30–60 °C, biosorbent dosage 0.1 – 0.5 g, and XO: EBT dye proportions 0 – 100 by weight %. Physicochemical characteristic studies were conducted by Fourier Transform Infrared (FTIR). The equilibrium uptake was increased with an increase in the initial dye concentrations in the solution. Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The experimental isotherms data were analyzed using Langmuir, Freundlich, Redlich-Peterson, and Toth isotherm equations. Thermodynamic parameters ∆Go, ∆Ho, and ∆So were calculated indicating that the biosorption of Xo and EBT dye is a spontaneous and endothermic process. The Langmuir model gave the best fit by higher correlation coefficient (R2 =0.9971) for both biosorbents at optimum circumstances as pH 3, temperature 30°C, dosage 0.5 g for chemically activated Cocos nucifera and 0.4 g for chemically activated mango seeds it assumes as monolayer adsorption. The maximum dye removal efficiency was determined as 79.75% with chemically activated mango seeds compared to chemically activated Cocos nucifera. In summary, this research work showed that chemically modified activated mango seed can be effectively used as a promising low-cost biosorbent for the removal of different XO and EBT mixed dye combinations from aqueous solutions.

Keywords: mixed dye proportions, xylenol orange and eriochrome black t, chemically activated cocos nucifera and mango seed, kinetic, isotherm and thermodynamic studies, FTIR

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26 Synthetic Bis(2-Pyridylmethyl)Amino-Chloroacetyl Chloride- Ethylenediamine-Grafted Graphene Oxide Sheets Combined with Magnetic Nanoparticles: Remove Metal Ions and Catalytic Application

Authors: Laroussi Chaabane, Amel El Ghali, Emmanuel Beyou, Mohamed Hassen V. Baouab

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In this research, the functionalization of graphene oxide sheets by ethylenediamine (EDA) was accomplished and followed by the grafting of bis(2-pyridylmethyl) amino group (BPED) onto the activated graphene oxide sheets in the presence of chloroacetylchloride (CAC) and then combined with magnetic nanoparticles (Fe₃O₄NPs) to produce a magnetic graphene-based composite [(Go-EDA-CAC)@Fe₃O₄NPs-BPED]. The physicochemical properties of [(Go-EDA-CAC)@Fe₃O₄NPs-BPED] composites were investigated by Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA). Additionally, the catalysts can be easily recycled within ten seconds by using an external magnetic field. Moreover, [(Go-EDA-CAC)@Fe₃O₄NPs-BPED] was used for removing Cu(II) ions from aqueous solutions using a batch process. The effect of pH, contact time and temperature on the metal ions adsorption were investigated, however weakly dependent on ionic strength. The maximum adsorption capacity values of Cu(II) on the [(Go-EDA-CAC)@Fe₃O₄NPs-BPED] at the pH of 6 is 3.46 mmol.g⁻¹. To examine the underlying mechanism of the adsorption process, pseudo-first, pseudo-second-order, and intraparticle diffusion models were fitted to experimental kinetic data. Results showed that the pseudo-second-order equation was appropriate to describe the Cu (II) adsorption by [(Go-EDA-CAC)@Fe₃O₄NPs-BPED]. Adsorption data were further analyzed by the Langmuir, Freundlich, and Jossens adsorption approaches. Additionally, the adsorption properties of the [(Go-EDA-CAC)@Fe₃O₄NPs-BPED], their reusability (more than 6 cycles) and durability in the aqueous solutions open the path to removal of Cu(II) from water solution. Based on the results obtained, we report the activity of Cu(II) supported on [(Go-EDA-CAC)@Fe₃O₄NPs-BPED] as a catalyst for the cross-coupling of symmetric alkynes.

Keywords: graphene, magnetic nanoparticles, adsorption kinetics/isotherms, cross coupling

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25 Batch and Fixed-Bed Studies of Ammonia Treated Coconut Shell Activated Carbon for Adsorption of Benzene and Toluene

Authors: Jibril Mohammed, Usman Dadum Hamza, Muhammad Idris Misau, Baba Yahya Danjuma, Yusuf Bode Raji, Abdulsalam Surajudeen

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Volatile organic compounds (VOCs) have been reported to be responsible for many acute and chronic health effects and environmental degradations such as global warming. In this study, a renewable and low-cost coconut shell activated carbon (PHAC) was synthesized and treated with ammonia (PHAC-AM) to improve its hydrophobicity and affinity towards VOCs. Removal efficiencies and adsorption capacities of the ammonia treated activated carbon (PHAC-AM) for benzene and toluene were carried out through batch and fixed-bed studies respectively. Langmuir, Freundlich and Tempkin adsorption isotherms were tested for the adsorption process and the experimental data were best fitted by Langmuir model and least fitted by Tempkin model; the favourability and suitability of fitness were validated by equilibrium parameter (RL) and the root square mean deviation (RSMD). Judging by the deviation of the predicted values from the experimental values, pseudo-second-order kinetic model best described the adsorption kinetics than the pseudo-first-order kinetic model for the two VOCs on PHAC and PHAC-AM. In the fixed-bed study, the effect of initial VOC concentration, bed height and flow rate on benzene and toluene adsorption were studied. The highest bed capacities of 77.30 and 69.40 mg/g were recorded for benzene and toluene respectively; at 250 mg/l initial VOC concentration, 2.5 cm bed height and 4.5 ml/min flow rate. The results of this study revealed that ammonia treated activate carbon (PHAC-AM) is a sustainable adsorbent for treatment of VOCs in polluted waters.

Keywords: volatile organic compounds, equilibrium and kinetics studies, batch and fixed bed study, bio-based activated carbon

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24 Engineered Bio-Coal from Pressed Seed Cake for Removal of 2, 4, 6-Trichlorophenol with Parametric Optimization Using Box–Behnken Method

Authors: Harsha Nagar, Vineet Aniya, Alka Kumari, Satyavathi B.

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In the present study, engineered bio-coal was produced from pressed seed cake, which otherwise is non-edible in origin. The production process involves a slow pyrolysis wherein, based on the optimization of process parameters; a substantial reduction in H/C and O/C of 77% was achieved with respect to the original ratio of 1.67 and 0.8, respectively. The bio-coal, so the product was found to have a higher heating value of 29899 kJ/kg with surface area 17 m²/g and pore volume of 0.002 cc/g. The functional characterization of bio-coal and its subsequent modification was carried out to enhance its active sites, which were further used as an adsorbent material for removal of 2,4,6-Trichlorophenol (2,4,6-TCP) herbicide from the aqueous stream. The point of zero charge for the bio-coal was found to be pH < 3 where its surface is positively charged and attracts anions resulting in the maximum 2, 4, 6-TCP adsorption at pH 2.0. The parametric optimization of the adsorption process was studied based on the Box-Behken design with the desirability approach. The results showed optimum values of adsorption efficiency of 74.04% and uptake capacity of 118.336 mg/g for an initial metal concentration of 250 mg/l and particle size of 0.12 mm at pH 2.0 and 1 g/L of bio-coal loading. Negative Gibbs free energy change values indicated the feasibility of 2,4,6-TCP adsorption on biochar. Decreasing the ΔG values with the rise in temperature indicated high favourability at low temperatures. The equilibrium modeling results showed that both isotherms (Langmuir and Freundlich) accurately predicted the equilibrium data, which may be attributed to the different affinity of the functional groups of bio-coal for 2,4,6-TCP removal. The possible mechanism for 2,4,6-TCP adsorption is found to be physisorption (pore diffusion, p*_p electron donor-acceptor interaction, H-bonding, and van der Waals dispersion forces) and chemisorption (phenolic and amine groups chemical bonding) based on the kinetics data modeling.

Keywords: engineered biocoal, 2, 4, 6-trichlorophenol, box behnken design, biosorption

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23 Effects of pH, Load Capacity and Contact Time in the Sulphate Sorption onto a Functionalized Mesoporous Structure

Authors: Jaime Pizarro, Ximena Castillo

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The intensive use of water in agriculture, industry, human consumption and increasing pollution are factors that reduce the availability of water for future generations; the challenge is to advance in sustainable and low-cost solutions to reuse water and to facilitate the availability of the resource in quality and quantity. The use of new low-cost materials with sorbent capacity for pollutants is a solution that contributes to the improvement and expansion of water treatment and reuse systems. Fly ash, a residue from the combustion of coal in power plants that is produced in large quantities in newly industrialized countries, contains a high amount of silicon oxides and aluminum oxides, whose properties can be used for the synthesis of mesoporous materials. Properly functionalized, this material allows obtaining matrixes with high sorption capacity. The mesoporous materials have a large surface area, thermal and mechanical stability, uniform porous structure, and high sorption and functionalization capacities. The goal of this study was to develop hexagonal mesoporous siliceous material (HMS) for the adsorption of sulphate from industrial and mining waters. The silica was extracted from fly ash after calcination at 850 ° C, followed by the addition of water. The mesoporous structure has a surface area of 282 m2 g-1 and a size of 5.7 nm and was functionalized with ethylene diamine through of a self-assembly method. The material was characterized by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The capacity of sulphate sorption was evaluated according to pH, maximum load capacity and contact time. The sulphate maximum adsorption capacity was 146.1 mg g-1, which is three times higher than commercial sorbents. The kinetic data were fitted according to a pseudo-second order model with a high coefficient of linear regression at different initial concentrations. The adsorption isotherm that best fitted the experimental data was the Freundlich model.

Keywords: fly ash, mesoporous siliceous, sorption, sulphate

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22 BTEX Removal from Water: A Comparative Analysis of Efficiency of Low Cost Adsorbents and Granular Activated Carbon

Authors: Juliet Okoli

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The removal of BTEX (Benzene, toluene, Ethylbenzene and p-Xylene) from water by orange peel and eggshell compared to GAC were investigated. The influence of various factors such as contact time, dosage and pH on BTEX removal by virgin orange peel and egg shell were accessed using the batch adsorption set-up. These were also compared to that of GAC which serves as a benchmark for this study. Further modification (preparation of Activated carbon) of these virgin low-cost adsorbents was also carried out. The batch adsorption result showed that the optimum contact time, dosage and pH for BTEX removal by virgin LCAs were 180 minutes, 0.5g and 7 and that of GAC was 30mintues, 0.2g and 7. The maximum adsorption capacity for total BTEX showed by orange peel and egg shell were 42mg/g and 59mg/g respectively while that of GAC was 864mg/g. The adsorbent preference for adsorbate were in order of X>E>T>B. A comparison of batch and column set-up showed that the batch set-up was more efficient than the column set-up. The isotherm data for the virgin LCA and GAC prove to fit the Freundlich isotherm better than the Langmuir model, which produced n values >1 in case of GAC and n< 1 in case of virgin LCAs; indicating a more appropriate adsorption of BTEX onto the GAC. The adsorption kinetics for the three studied adsorbents were described well by the pseudo-second order, suggesting chemisorption as the rate limiting step. This was further confirmed by desorption study, as low levels of BTEX (<10%) were recovered from the spent adsorbents especially for GAC (<3%). Further activation of the LCAs which was compared to the virgin LCAs, revealed that the virgin LCAs had minor higher adsorption capacity than the activated LCAs. Economic analysis revealed that the total cost required to clean-up 9,600m3 of BTEX contaminated water using LCA was just 2.8% lesser than GAC, a difference which could be considered negligible. However, this area still requires a more detailed cost-benefit analysis, and if similar conclusions are reached; a low-cost adsorbent, easy to obtain are still promising adsorbents for BTEX removal from aqueous solution; however, the GAC are still more superior to these materials.

Keywords: activated carbon, BTEX removal, low cost adsorbents, water treatment

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21 Removal of Cr (VI) from Water through Adsorption Process Using GO/PVA as Nanosorbent

Authors: Syed Hadi Hasan, Devendra Kumar Singh, Viyaj Kumar

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Cr (VI) is a known toxic heavy metal and has been considered as a priority pollutant in water. The effluent of various industries including electroplating, anodizing baths, leather tanning, steel industries and chromium based catalyst are the major source of Cr (VI) contamination in the aquatic environment. Cr (VI) show high mobility in the environment and can easily penetrate cell membrane of the living tissues to exert noxious effects. The Cr (VI) contamination in drinking water causes various hazardous health effects to the human health such as cancer, skin and stomach irritation or ulceration, dermatitis, damage to liver, kidney circulation and nerve tissue damage. Herein, an attempt has been done to develop an efficient adsorbent for the removal of Cr (VI) from water. For this purpose nanosorbent composed of polyvinyl alcohol functionalized graphene oxide (GO/PVA) was prepared. Thus, obtained GO/PVA was characterized through FTIR, XRD, SEM, and Raman Spectroscopy. As prepared nanosorbent of GO/PVA was utilized for the removal Cr (VI) in batch mode experiment. The process variables such as contact time, initial Cr (VI) concentration, pH, and temperature were optimized. The maximum 99.8 % removal of Cr (VI) was achieved at initial Cr (VI) concentration 60 mg/L, pH 2, temperature 35 °C and equilibrium was achieved within 50 min. The two widely used isotherm models viz. Langmuir and Freundlich were analyzed using linear correlation coefficient (R2) and it was found that Langmuir model gives best fit with high value of R2 for the data of present adsorption system which indicate the monolayer adsorption of Cr (VI) on the GO/PVA. Kinetic studies were also conducted using pseudo-first order and pseudo-second order models and it was observed that chemosorptive pseudo-second order model described the kinetics of current adsorption system in better way with high value of correlation coefficient. Thermodynamic studies were also conducted and results showed that the adsorption was spontaneous and endothermic in nature.

Keywords: adsorption, GO/PVA, isotherm, kinetics, nanosorbent, thermodynamics

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20 Development of Cobalt Doped Alumina Hybrids for Adsorption of Textile Effluents

Authors: Uzaira Rafique, Kousar Parveen

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The discharge volume and composition of Textile effluents gains scientific concern due to its hazards and biotoxcity of azo dyes. Azo dyes are non-biodegradable due to its complex molecular structure and recalcitrant nature. Serious attempts have been made to synthesize and develop new materials to combat the environmental problems. The present study is designed for removal of a range of azo dyes (Methyl orange, Congo red and Basic fuchsine) from synthetic aqueous solutions and real textile effluents. For this purpose, Metal (cobalt) doped alumina hybrids are synthesized and applied as adsorbents in the batch experiment. Two different aluminium precursor (aluminium nitrate and spent aluminium foil) and glucose are mixed following sol gel method to get hybrids. The synthesized materials are characterized for surface and bulk properties using FTIR, SEM-EDX and XRD techniques. The characterization of materials under FTIR revealed that –OH (3487-3504 cm-1), C-H (2935-2985 cm-1), Al-O (~ 800 cm-1), Al-O-C (~1380 cm-1), Al-O-Al (659-669 cm-1) groups participates in the binding of dyes onto the surface of hybrids. Amorphous shaped particles and elemental composition of carbon (23%-44%), aluminium (29%-395%), and oxygen (11%-20%) is demonstrated in SEM-EDX micrograph. Time-dependent batch-experiments under identical experimental parameters showed 74% congo red, 68% methyl orange and 85% maximum removal of basic fuchsine onto the surface of cobalt doped alumina hybrids probably through the ion-exchange mechanism. The experimental data when treated with adsorption models is found to have good agreement with pseudo second order kinetic and freundlich isotherm for adsorption process. The present study concludes the successful synthesis of novel and efficient cobalt doped alumina hybrids providing environmental friendly and economical alternative to the commercial adsorbents for the treatment of industrial effluents.

Keywords: alumina hybrid, adsorption, dopant, isotherm, kinetic

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19 Equilibrium, Kinetics, and Thermodynamic Studies on Heavy Metal Biosorption by Trichoderma Species

Authors: Sobia Mushtaq, Firdaus E. Bareen, Asma Tayyeb

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This study conducted to investigate the metal biosorption potential of indigenous Trichoderma species (T. harzianum KS05T01, T. longibrachiatum KS09T03, Trichoderma sp KS17T09., T. viridi KS17T011, T. atrobruneo KS21T014, and T. citrinoviride) that have been isolated from contaminated soil of Kasur Tannery Waste Management Agency. The effect of different biosorption parameters as initial metal ion concentration, pH, contact time , and temperature of incubation was investigated on the biosorption potential of these species. The metal removal efficiency and (E%) and metal uptake capacity (mg/g) increased along with the increase of initial metal concentration in media. The Trichoderma species can tolerate and survive under heavy metal stress up to 800mg/L. Among the two isotherm models were applied on the biosorption data, Langmuir isotherm model and Freundlich isotherm model, maximum correlation coefficients values (R 2 ) of 1was found for Langmuir model, which showed the better fitted model for the Trichoderma biosorption. The metal biosorption was increased with the increase of temperature and pH of the media. The maximum biosorption was observed between 25-30 o C and at pH 6.-7.5, while the biosorption rate was increased from 3-6 days of incubation, and then the rate of biosorption was slowed down. The biosorption data was better fitted for Pseudo kinetic first order during the initial days of biosorption. Thermodynamic parameters as standard Gibbs free energy (G), standard enthalpy change (H), and standard entropy (S) were calculated. The results confirmed the heavy metal biosorption by Trichoderma species was endothermic and spontaneous reaction in nature. The FTIR spectral analysis and SEM-EDX analysis of the treated and controlled mycelium revealed the changes in the active functional sites and morphological variations of the outer surface. The data analysis envisaged that high metal tolerance exhibited by Trichoderma species indicates its potential as efficacious and successful mediator for bioremediation of the heavy metal polluted environments.

Keywords: heavy metal, fungal biomass, biosorption, kinetics

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18 Adsorptive Removal of Cd(II) Ions from Aqueous Systems by Wood Ash-Alginate Composite Beads

Authors: Tichaona Nharingo, Hope Tauya, Mambo Moyo

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Wood ash has been demonstrated to have favourable adsorption capacity for heavy metal ions but suffers the application problem of difficult to separate/isolate from the batch adsorption systems. Fabrication of wood ash beads using multifunctional group and non-toxic carbohydrate, alginate, may improve the applicability of wood ash in environmental pollutant remediation. In this work, alginate-wood ash beads (AWAB) were fabricated and applied to the removal of cadmium ions from aqueous systems. The beads were characterized by FTIR, TGA/DSC, SEM-EDX and their pHZPC before and after the adsorption of Cd(II) ions. Important adsorption parameters i.e. pH, AWAB dosage, contact time and ionic strength were optimized and the effect of initial concentration of Cd(II) ions to the adsorption process was established. Adsorption kinetics, adsorption isotherms, adsorption mechanism and application of AWAB to real water samples spiked with Cd(II) ions were ascertained. The composite adsorbent was characterized by a heterogeneous macro pore surface comprising of metal oxides, multiple hydroxyl groups and carbonyl groups that were involved in electrostatic interaction and Lewis acid-base interactions with the Cd(II) ions. The pseudo second order and the Freundlich isotherm models best fitted the adsorption kinetics and isotherm data respectively suggesting chemical sorption process and surface heterogeneity. The presence of Pb(II) ions inhibited the adsorption of Cd(II) ions (reduced by 40 %) attributed to the competition for the adsorption sites. The Cd(II) loaded beads could be regenerated using 0.1 M HCl and could be applied to four sorption-desorption cycles without significant loss in its initial adsorption capacity. The high maximum adsorption capacity, stability, selectivity and reusability of AWAB make the adsorbent ideal for application in the removal of Cd(II) ions from real water samples. Column type adsorption experiments need to be explored to establish the potential of the adsorbent in removing Cd(II) ions using continuous flow systems.

Keywords: adsorption, Cd(II) ions, regeneration, wastewater, wood ash-alginate beads

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17 Covalent Binding of Cysteine to a Sol-Gel Material for Cadmium Biosorption from Aqueous Solutions

Authors: Claudiu Marcu, Cristina Paul, Adelina Andelescu, Corneliu Mircea Davidescu, Francisc Péter

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Heavy metal pollution has become a more serious environmental problem in the last several decades as a result of its toxicity and insusceptibility to the environment. Methods for removing metal ions from aqueous solution mainly consist of physical, chemical and biochemical procedures. Biosorption is defined as the removal of metal or metalloid species, compounds and particulates from solution by a biological material. Biosorption represents a very attractive method for the removal of toxic metal ions from aqueous effluents because it uses the ability of various biomass to bind the metal ions without the risk of releasing other toxic chemical compounds into the environment. The problem with using biomass or living cells as biosorbents is that their regeneration/reuse is often either impossible or very laborious. One of the most common chelating group found in biosorbents is the thiol group in cysteine. Therefore, we immobilized cysteine using covalent binding using glutaraldehyde as a linker on a synthetic sol-gel support obtained using 3-amino-propyl-trimetoxysilane and trimetoxysilane as precursors. The obtained adsorbents were used for removal of cadmium from aqueous solutions and the removal capacity was investigated in relation to the composition of the sol-gel hybrid composite, the loading of the biomolecule and the physical parameters of the biosorption process. In the same conditions, the bare sol-gel support without cysteine had no Cd removal effect, while the adsorbent with cysteine had an adsorption capacity up to 25.8 mg Cd/g adsorbent at pH 2.0 and 119 mg Cd/g adsorbent at pH 6.6, depending on cadmium concentration and adsorption conditions. We used atomic adsorption spectrometry to assess the cadmium concentration in the samples after the biosorbtion process. The parameters for the Freundlich and Langmuir adsorption isotherms where calculated from plotting the results of the adsorption experiments. The results for cysteine immobilization show a good loading capacity of the sol-gel support which indicates it could be used to immobilize metal binding proteins and by doing so boosting the heavy metal adsorption capacity of the biosorbent.

Keywords: biosorbtion, cadmium, cysteine covalent binding, sol-gel

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16 Removal of Nickel Ions from Industrial Effluents by Batch and Column Experiments: A Comparison of Activated Carbon with Pinus Roxburgii Saw Dust

Authors: Sardar Khana, Zar Ali Khana

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Rapid industrial development and urbanization contribute a lot to wastewater discharge. The wastewater enters into natural aquatic ecosystems from industrial activities and considers as one of the main sources of water pollution. Discharge of effluents loaded with heavy metals into the surrounding environment has become a key issue regarding human health risk, environment, and food chain contamination. Nickel causes fatigue, cancer, headache, heart problems, skin diseases (Nickel Itch), and respiratory disorders. Nickel compounds such as Nickel Sulfide and Nickel oxides in industrial environment, if inhaled, have an association with an increased risk of lung cancer. Therefore the removal of Nickel from effluents before discharge is necessary. Removal of Nickel by low-cost biosorbents is an efficient method. This study was aimed to investigate the efficiency of activated carbon and Pinusroxburgiisaw dust for the removal of Nickel from industrial effluents using commercial Activated Carbon, and raw P.roxburgii saw dust. Batch and column adsorption experiments were conducted for the removal of Nickel. The study conducted indicates that removal of Nickel greatly dependent on pH, contact time, Nickel concentration, and adsorbent dose. Maximum removal occurred at pH 9, contact time of 600 min, and adsorbent dose of 1 g/100 mL. The highest removal was 99.62% and 92.39% (pH based), 99.76% and 99.9% (dose based), 99.80% and 100% (agitation time), 92% and 72.40% (Ni Conc. based) for P.roxburgii saw dust and activated Carbon, respectively. Similarly, the Ni removal in column adsorption was 99.77% and 99.99% (bed height based), 99.80% and 99.99% (Concentration based), 99.98%, and 99.81% (flow rate based) during column studies for Nickel using P.Roxburgiisaw dust and activated carbon, respectively. Results were compared with Freundlich isotherm model, which showed “r2” values of 0.9424 (Activated carbon) and 0.979 (P.RoxburgiiSaw Dust). While Langmuir isotherm model values were 0.9285 (Activated carbon) and 0.9999 (P.RoxburgiiSaw Dust), the experimental results were fitted to both the models. But the results were in close agreement with Langmuir isotherm model.

Keywords: nickel removal, batch, and column, activated carbon, saw dust, plant uptake

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15 Adsorptive Removal of Methylene Blue Dye from Aqueous Solutions by Leaf and Stem Biochar Derived from Lantana camara: Adsorption Kinetics, Equilibrium, Thermodynamics and Possible Mechanism

Authors: Deepa Kundu, Prabhakar Sharma, Sayan Bhattacharya, Jianying Shang

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The discharge of dye-containing effluents in the water bodies has raised concern due to the potential hazards related to their toxicity in the environment. There are various treatment technologies available for the removal of dyes from wastewaters. The use of biosorbent to remove dyes from wastewater is one of the effective and inexpensive techniques. In the study, the adsorption of phenothiazine dye methylene blue onto biosorbent prepared from Lantana camara L. has been studied in aqueous solutions. The batch adsorption experiments were conducted and the effects of various parameters such as pH (3-12), contact time, adsorbent dose (100-400 mg/L), initial dye concentration (5-20 mg/L), and temperature (303, 313 and 323 K) were investigated. The prepared leaf (BCL600) and shoot (BCS600) biochar of Lantana were characterized using FTIR, SEM, elemental analysis, and zeta potential (pH~7). A comparison between the adsorption potential of both the biosorbent was also evaluated. The results indicated that the amount of methylene blue dye (mg/g) adsorbed onto the surface of biochar was highly dependent on the pH of the dye solutions as it increased with an increase in pH from 3 to 12. It was observed that the dye treated with BCS600 and BCL600 attained an equilibrium within 60 and 100 minutes, respectively. The rate of the adsorption process was determined by performing the Lagergren pseudo-first-order and pseudo-second-order kinetics. It was found that dye treated with both BCS600 and BCL600 followed pseudo-second-order kinetics implying the multi-step nature of the adsorption process involving external adsorption and diffusion of dye molecules into the interior of the adsorbents. The data obtained from batch experiments were fitted well with Langmuir and Freundlich isotherms (R² > 0.98) to indicate the multilayer adsorption of dye over the biochar surfaces. The thermodynamic studies revealed that the adsorption process is favourable, spontaneous, and endothermic in nature. Based on the results, the inexpensive and easily available Lantana camara biomass can be used to remove methylene blue dye from wastewater. It can also help in managing the growth of the notorious weed in the environment.

Keywords: adsorption kinetics, biochar, Lantana camara, methylene blue dye, possible mechanism, thermodynamics

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14 Bio-Remediation of Lead-Contaminated Water Using Adsorbent Derived from Papaya Peel

Authors: Sahar Abbaszadeh, Sharifah Rafidah Wan Alwi, Colin Webb, Nahid Ghasemi, Ida Idayu Muhamad

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Toxic heavy metal discharges into environment due to rapid industrialization is a serious pollution problem that has drawn global attention towards their adverse impacts on both the structure of ecological systems as well as human health. Lead as toxic and bio-accumulating elements through the food chain, is regularly entering to water bodies from discharges of industries such as plating, mining activities, battery manufacture, paint manufacture, etc. The application of conventional methods to degrease and remove Pb(II) ion from wastewater is often restricted due to technical and economic constrains. Therefore, the use of various agro-wastes as low-cost bioadsorbent is found to be attractive since they are abundantly available and cheap. In this study, activated carbon of papaya peel (AC-PP) (as locally available agricultural waste) was employed to evaluate its Pb(II) uptake capacity from single-solute solutions in sets of batch mode experiments. To assess the surface characteristics of the adsorbents, the scanning electron microscope (SEM) coupled with energy disperse X-ray (EDX), and Fourier transform infrared spectroscopy (FT-IR) analysis were utilized. The removal amount of Pb(II) was determined by atomic adsorption spectrometry (AAS). The effects of pH, contact time, the initial concentration of Pb(II) and adsorbent dosage were investigated. The pH value = 5 was observed as optimum solution pH. The optimum initial concentration of Pb(II) in the solution for AC-PP was found to be 200 mg/l where the amount of Pb(II) removed was 36.42 mg/g. At the agitating time of 2 h, the adsorption processes using 100 mg dosage of AC-PP reached equilibrium. The experimental results exhibit high capability and metal affinity of modified papaya peel waste with removal efficiency of 93.22 %. The evaluation results show that the equilibrium adsorption of Pb(II) was best expressed by Freundlich isotherm model (R2 > 0.93). The experimental results confirmed that AC-PP potentially can be employed as an alternative adsorbent for Pb(II) uptake from industrial wastewater for the design of an environmentally friendly yet economical wastewater treatment process.

Keywords: activated carbon, bioadsorption, lead removal, papaya peel, wastewater treatment

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13 Synthesis of High-Pressure Performance Adsorbent from Coconut Shells Polyetheretherketone for Methane Adsorption

Authors: Umar Hayatu Sidik

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Application of liquid base petroleum fuel (petrol and diesel) for transportation fuel causes emissions of greenhouse gases (GHGs), while natural gas (NG) reduces the emissions of greenhouse gases (GHGs). At present, compression and liquefaction are the most matured technology used for transportation system. For transportation use, compression requires high pressure (200–300 bar) while liquefaction is impractical. A relatively low pressure of 30-40 bar is achievable by adsorbed natural gas (ANG) to store nearly compressed natural gas (CNG). In this study, adsorbents for high-pressure adsorption of methane (CH4) was prepared from coconut shells and polyetheretherketone (PEEK) using potassium hydroxide (KOH) and microwave-assisted activation. Design expert software version 7.1.6 was used for optimization and prediction of preparation conditions of the adsorbents for CH₄ adsorption. Effects of microwave power, activation time and quantity of PEEK on the adsorbents performance toward CH₄ adsorption was investigated. The adsorbents were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric (TG) and derivative thermogravimetric (DTG) and scanning electron microscopy (SEM). The ideal CH4 adsorption capacities of adsorbents were determined using volumetric method at pressures of 5, 17, and 35 bar at an ambient temperature and 5 oC respectively. Isotherm and kinetics models were used to validate the experimental results. The optimum preparation conditions were found to be 15 wt% amount of PEEK, 3 minutes activation time and 300 W microwave power. The highest CH4 uptake of 9.7045 mmol CH4 adsorbed/g adsorbent was recorded by M33P15 (300 W of microwave power, 3 min activation time and 15 wt% amount of PEEK) among the sorbents at an ambient temperature and 35 bar. The CH4 equilibrium data is well correlated with Sips, Toth, Freundlich and Langmuir. Isotherms revealed that the Sips isotherm has the best fit, while the kinetics studies revealed that the pseudo-second-order kinetic model best describes the adsorption process. In all scenarios studied, a decrease in temperature led to an increase in adsorption of both gases. The adsorbent (M33P15) maintained its stability even after seven adsorption/desorption cycles. The findings revealed the potential of coconut shell-PEEK as CH₄ adsorbents.

Keywords: adsorption, desorption, activated carbon, coconut shells, polyetheretherketone

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12 A Study on Adsorption Ability of MnO2 Nanoparticles to Remove Methyl Violet Dye from Aqueous Solution

Authors: Zh. Saffari, A. Naeimi, M. S. Ekrami-Kakhki, Kh. Khandan-Barani

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The textile industries are becoming a major source of environmental contamination because an alarming amount of dye pollutants are generated during the dyeing processes. Organic dyes are one of the largest pollutants released into wastewater from textile and other industrial processes, which have shown severe impacts on human physiology. Nano-structure compounds have gained importance in this category due their anticipated high surface area and improved reactive sites. In recent years several novel adsorbents have been reported to possess great adsorption potential due to their enhanced adsorptive capacity. Nano-MnO2 has great potential applications in environment protection field and has gained importance in this category because it has a wide variety of structure with large surface area. The diverse structures, chemical properties of manganese oxides are taken advantage of in potential applications such as adsorbents, sensor catalysis and it is also used for wide catalytic applications, such as degradation of dyes. In this study, adsorption of Methyl Violet (MV) dye from aqueous solutions onto MnO2 nanoparticles (MNP) has been investigated. The surface characterization of these nano particles was examined by Particle size analysis, Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy and X-Ray Diffraction (XRD). The effects of process parameters such as initial concentration, pH, temperature and contact duration on the adsorption capacities have been evaluated, in which pH has been found to be most effective parameter among all. The data were analyzed using the Langmuir and Freundlich for explaining the equilibrium characteristics of adsorption. And kinetic models like pseudo first- order, second-order model and Elovich equation were utilized to describe the kinetic data. The experimental data were well fitted with Langmuir adsorption isotherm model and pseudo second order kinetic model. The thermodynamic parameters, such as Free energy of adsorption (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were also determined and evaluated.

Keywords: MnO2 nanoparticles, adsorption, methyl violet, isotherm models, kinetic models, surface chemistry

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11 Evaluation of Natural Waste Materials for Ammonia Removal in Biofilters

Authors: R. F. Vieira, D. Lopes, I. Baptista, S. A. Figueiredo, V. F. Domingues, R. Jorge, C. Delerue-matos, O. M. Freitas

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Odours are generated in municipal solid wastes management plants as a result of decomposition of organic matter, especially when anaerobic degradation occurs. Information was collected about the substances and respective concentration in the surrounding atmosphere of some management plants. The main components which are associated with these unpleasant odours were identified: ammonia, hydrogen sulfide and mercaptans. The first is the most common and the one that presents the highest concentrations, reaching values of 700 mg/m3. Biofiltration, which involves simultaneously biodegradation, absorption and adsorption processes, is a sustainable technology for the treatment of these odour emissions when a natural packing material is used. The packing material should ideally be cheap, durable, and allow the maximum microbiological activity and adsorption/absorption. The presence of nutrients and water is required for biodegradation processes. Adsorption and absorption are enhanced by high specific surface area, high porosity and low density. The main purpose of this work is the exploitation of natural waste materials, locally available, as packing media: heather (Erica lusitanica), chestnut bur (from Castanea sativa), peach pits (from Prunus persica) and eucalyptus bark (from Eucalyptus globulus). Preliminary batch tests of ammonia removal were performed in order to select the most interesting materials for biofiltration, which were then characterized. The following physical and chemical parameters were evaluated: density, moisture, pH, buffer and water retention capacity. The determination of equilibrium isotherms and the adjustment to Langmuir and Freundlich models was also performed. Both models can fit the experimental results. Based both in the material performance as adsorbent and in its physical and chemical characteristics, eucalyptus bark was considered the best material. It presents a maximum adsorption capacity of 0.78±0.45 mol/kg for ammonia. The results from its characterization are: 121 kg/m3 density, 9.8% moisture, pH equal to 5.7, buffer capacity of 0.370 mmol H+/kg of dry matter and water retention capacity of 1.4 g H2O/g of dry matter. The application of natural materials locally available, with little processing, in biofiltration is an economic and sustainable alternative that should be explored.

Keywords: ammonia removal, biofiltration, natural materials, odour control

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10 Removal of Methylene Blue from Aqueous Solution by Adsorption onto Untreated Coffee Grounds

Authors: N. Azouaou, H. Mokaddem, D. Senadjki, K. Kedjit, Z. Sadaoui

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Introduction: Water contamination caused by dye industries, including food, leather, textile, plastic, cosmetics, paper-making, printing and dye synthesis, has caused more and more attention, since most dyes are harmful to human being and environments. Untreated coffee grounds were used as a high-efficiency adsorbent for the removal of a cationic dye (methylene blue, MB) from aqueous solution. Characterization of the adsorbent was performed using several techniques such as SEM, surface area (BET), FTIR and pH zero charge. The effects of contact time, adsorbent dose, initial solution pH and initial concentration were systematically investigated. Results showed the adsorption kinetics followed the pseudo-second-order kinetic model. Langmuir isotherm model is in good agreement with the experimental data as compared to Freundlich and D–R models. The maximum adsorption capacity was found equal to 52.63mg/g. In addition, the possible adsorption mechanism was also proposed based on the experimental results. Experimental: The adsorption experiments were carried out in batch at room temperature. A given mass of adsorbent was added to methylene blue (MB) solution and the entirety was agitated during a certain time. The samples were carried out at quite time intervals. The concentrations of MB left in supernatant solutions after different time intervals were determined using a UV–vis spectrophotometer. The amount of MB adsorbed per unit mass of coffee grounds (qt) and the dye removal efficiency (R %) were evaluated. Results and Discussion: Some chemical and physical characteristics of coffee grounds are presented and the morphological analysis of the adsorbent was also studied. Conclusions: The good capacity of untreated coffee grounds to remove MB from aqueous solution was demonstrated in this study, highlighting its potential for effluent treatment processes. The kinetic experiments show that the adsorption is rapid and maximum adsorption capacities qmax= 52.63mg/g achieved in 30min. The adsorption process is a function of the adsorbent concentration, pH and metal ion concentration. The optimal parameters found are adsorbent dose m=5g, pH=5 and ambient temperature. FTIR spectra showed that the principal functional sites taking part in the sorption process included carboxyl and hydroxyl groups.

Keywords: adsorption, methylene blue, coffee grounds, kinetic study

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