Retention dynamics of multi-metal contaminants from pond ash slurry onto fine grained soil

The coal fly ashes contain high concentration of toxic metals. The sorption plays crucial part to retard the movement of contaminants through the liner. In the present investigation to examine the potential of fine-grained soil as liner material, obtained from bank of River Ganga, was assessed in terms of its adsorption capability. Batch adsorption of Pb(II) and Cr(VI) were performed. Maximum adsorption of Cr(VI) (65.76%) at pH 3 for adsorbate and adsorbent dose of 5 ​mg/L and 2 ​g/L and maximum adsorption of Pb(II) (96.84%) at pH 5 for adsorbate and adsorbent dose of 5 ​mg/L and 1.5 ​g/L, respectively, were observed. Adsorption of Pb(II) and Cr(VI) follow Freundlich isotherm equation. The soil column studies were performed at various bed heights (2, 3 and 5 ​cm) in down flow mode. The tracer studies were conducted using NaCl to estimate the hydrodynamic parameters and they were considered as input parameters for modelling of fate and transport of contaminants in soil using HYDRUS 1D software for assessing the potential use of soil as liner material in ash pond structures.     

Highly efficient,economic, and recyclable glutathione decorated magnetically separable nanocomposite for uranium(VI) adsorption from aqueous solution

A green and environment-friendly magnetically separable nanocomposite, glutathione@magnetite was fabricated sonochemically through the functionalization of Fe₃O₄ by glutathione which was well characterized using Fourier-transform infrared spectroscopy, ultravoilet-visible spectroscopy, scanning electron microscope, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermogravimetric analysis, vibrating sample magnetometer, Brunauer-Emmett-Teller, and high-resolution transmission electron microscope. The parameters affecting adsorption including pH, temperature, contact time, initial adsorbate concentration, and adsorbent amount were optimized by batch experiments. The magnetic glutathione@magnetite was applied for the removal of uranium(VI) in water with maximum adsorption capacity found to be 333.33 mg/g in 120 min at a neutral pH at 25 °C showing high efficiency for U(VI) ions. Furthermore, adsorption results obtained from UV-vis spectroscopy were validated by inductively coupled plasma optical emission spectroscopy. The thermodynamic parameters, viz Gibbs free energy (ΔGº), standard enthalpy change (ΔHº), and standard entropy change (ΔSº) of the process were calculated using the Langmuir constants. The pseudo-second-order kinetics model is seen to be applicable for describing the uptake process using a kinetics test. Moreover, desorption studies reveals that glutathione@magnetite can be used repeatedly, and removal efficiency shows only a small decrease after six cycles. Thus, glutathione@magnetite acts as a potential adsorbent for the removal of U(VI) from the water with great adsorption performance.     

Kinetics and equilibrium studies of adsorption of chromium(VI) ion from industrial wastewater using Chrysophyllum albidum (Sapotaceae) seed shells

A new biosorbent has been prepared by coating Chrysophyllum albidum (Sapotaceae) seed shells with chitosan and/or oxidizing agents such as sulfuric acid. This study investigated the technical feasibility of activated and modified activated C. albidum seed shells carbons for the adsorption of chromium(VI) from aqueous solution. The sorption process with respect to its equilibria and kinetics as well as the effects of pH, contact time, adsorbent mass, adsorbate concentration and particle size on adsorption was also studied. The most effective pH range was found to be between 4.5 and 5 for the sorption of the metal ion. The pseudo-first-order rate equation by Lagergren and pseudo-second-order rate equation were tested on the kinetic data, the adsorption process followed pseudo-second-order rate kinetics, also, isotherm data was analyzed for possible agreement with the Langmuir and Freundlich adsorption isotherms, the Freundlich and Langmuir models for dynamics of metal ion uptake proposed in this work fitted the experimental data reasonably well. However, equilibrium sorption data were better represented by Langmuir model than Freundlich. The adsorption capacity calculated from Langmuir isotherm was 84.31, 76.23 and 59.63 mg Cr(VI)/g at initial pH of 3.0 at 30 °C for the particle size of 1.00–1.25 mm with the use of 12.5, 16.5 and 2.1 g/L of CACASC, CCASC and ACASC adsorbent mass, respectively. This readily available adsorbent is efficient in the uptake of Cr(VI) ion in aqueous solution, thus, it could be an excellent alternative for the removal of heavy metals and organic matter from water and wastewater.     

Adsorption of Cr(VI) using activated neem leaves: kinetic studies

In the present study, adsorbent is prepared from neem leaves and used for Cr(VI) removal from aqueous solutions. Neem leaves are activated by giving heat treatment and with the use of concentrated hydrochloric acid (36.5 wt%). The activated neem leaves are further treated with 100 mmol of copper solution. Batch adsorption studies demonstrate that the adsorbent prepared from neem leaves has a significant capacity for adsorption of Cr(VI) from aqueous solution. The parameters investigated in this study include pH, contact time, initial Cr(VI) concentration and adsorbent dosage. The adsorption of Cr(VI) is found to be maximum (99%) at low values of pH in the range of 1-3. A small amount of the neem leaves adsorbent (10 g/l) could remove as much as 99% of Cr(VI) from a solution of initial concentration 50 mg/l. The adsorption process of Cr(VI) is tested with Langmuir isotherm model. Application of the Langmuir isotherm to the system yielded maximum adsorption capacity of 62.97 mg/g. The dimensionless equilibrium parameter, R _L, signifies a favorable adsorption of Cr(VI) on neem leaves adsorbent and is found to be between 0.0155 and 0.888 (0<R _L<1). The adsorption process follows second order kinetics and the corresponding rate constant is found to be 0.00137 g/(mg) (min).     

Chemical modification of expanded glass aggregate with N-Benzoyl-N′-(4-methylphenyl) thiourea (TTU) for the adsorptive removal of Cr(III) ion

In this study, the silylant agent 3-aminopropyl trimethoxysilane (APTES) was anchored on expanded glass aggregate (GA) to prepare a new adsorbent. N-Benzoyl-N′-(4-methylphenyl) thiourea (TTU) bonded to amino-functionalized GA adsorbent with reflux. Developed adsorbent (GA-APTES-TTU) was characterized using thermal analysis (TGA) and scanning electron microscopy (SEM). TGA and SEM studies indicated that modification of the glass aggregate (GA) surfaces was successfully performed. The adsorption studies exhibited that the GA-APTES-TTU could be efficiently used for the removal of Cr(III) from aqueous solutions. The effects of pH, adsorbent dosage, ion concentration, time, and temperature were investigated as adsorption parameters. The maximum removal of Cr(III) was observed at pH 4. The adsorption equilibrium was achieved in 120 min and adsorption of Cr(III) followed the Langmuir isotherm model. The maximum adsorption capacity for Cr(III) was 0.4305 mmol/g with GA-APTES-TTU. Thermodynamic parameters such as the standard free energy (ΔG^o), enthalpy change (ΔH°) and entropy change (ΔS°) were calculated in order to explain the mechanism of adsorption process. The thermodynamic data showed that Cr(III) adsorption was spontaneous, endothermic, and a physisorption reaction. In addition, the adsorption kinetic data fitted to the pseudo-second order model.     

Removal of Cr(VI) from water by cork waste

The biosorption by cork powder is considered as a promising method for heavy metal removal from industrial waste waters such as chromium tanning factories. The aim of this study is to evaluate the efficiency extent of this method using cork powder as a biosorbent for Cr(VI). The Fourier Transform Infrared spectroscopy (FTIR) analysis permits to distinguish the type of functional groups likely to participate in metal binding. A linear form of BET isotherms for all the three used temperatures (i.e., 25, 35 and 45 °C) and a pseudo-second-order equation of adsorption kinetics are obtained. Other experimental results highlight the meaningful influence of parameters such as contact time, pH, concentration of Cr(VI) and the adsorbent particle size on Cr(VI) adsorption. 97% of Cr(VI) has been removed under definite conditions particularly a particle size of diameter d < 0.08 mm and pH of 2–3 values.     

Thermodynamic analysis of sorption isotherms of chromium(VI) anionic species on reed biomass

A new sorbent material for removing Cr(VI) anionic species from aqueous solutions has been investigated. Adsorption equilibrium and thermodynamics of Cr(VI) anionic species onto reed biomass were studied at different initial concentrations, sorbent concentrations, pH levels, temperatures, and ionic strength. Equilibrium isotherm was analyzed by Langmuir model. The experimental sorption data fit the model very well. The maximum sorption capacity of Cr(VI) onto reed biomass was found to be 33 mg · g^?1. It was noted that the Cr(VI) adsorption by reed biomass decreased with increase in pH. An increase in temperature resulted in a higher Cr(VI) loading per unit weight of the adsorbent. Removal of Cr(VI) by reed biomass seems to be mainly by chemisorption. The change in entropy (ΔS^°) and heat of adsorption (ΔH^°) for Cr(VI) adsorption on reed biomass were estimated as 2205 kJ · kg^?1 · K^?1 and 822 kJ · kg^?1, respectively. The values of isosteric heat of adsorption varied with the surface loading of Cr(VI).     

Adsorption of Cr(VI) using cellulose microsphere-based adsorbent prepared by radiation-induced grafting

Cellulose microsphere (CMS) adsorbent was prepared by radiation-induced grafting of dimethylaminoethyl methacrylate (DMAEMA) onto CMS followed by a protonation process. The FTIR spectra analysis proved that PDMAEMA was grafted successfully onto CMS. The adsorption of Cr(VI) onto the resulting adsorbent was very fast, the equilibrium adsorption could be achieved within 15 min. The adsorption capacity strongly depended on the pH of the solution, which was attributed to the change of both the existed forms of Cr(VI) and the tertiary-ammonium group of PDMAEMA grafted CMS with the pH. A maximum Cr(VI) uptake (ca. 78 mg g^?1) was obtained as the pH was in the range of 3.0–6.0. However, even in strong acid media (pH 1.3), the adsorbents still showed a Cr(VI) uptake of 30 mg g^?1. The adsorption behavior of the resultant absorbent could be described with the Langmuir mode. This adsorbent has potential application for removing heavy metal ion pollutants (e.g. Cr(VI)) from wastewater.     

Removal of trace Cr(VI) from water using chitosan-iron nanowires in porous anodic alumina

Chitosan-iron nanowires in porous anodic alumina (PAA) have been successfully prepared under ambient conditions as an adsorbent. The adsorbent was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy and N₂-BET surface area. The results showed that PAA can disperse and protect Fe⁰ nanorods from oxidation. The adsorption characteristics of trace Cr(VI) onto adsorbent have been examined at different initial Cr(VI) concentrations with pH 5. Batch adsorption studies show that the removal percentage of adsorbent for the removal of trace Cr(VI) is strongly dependent on the initial Cr(VI) concentrations. Langmuir and Freundlich isotherm models were used to analyze the experiment data. The adsorption of trace Cr(VI) by adsorbent is well modeled by the Langmuir isotherm and the maximum adsorption capacity of Cr(VI) is calculated as 123.95 mg/g which is very closed to the experiment results. Intraparticle diffusion study shows that the intraparticle diffusion of adsorbent is not the sole rate-controlling step. The negative value of Gibbs free energy change, ΔG^o, indicated that the process of Cr(VI) onto adsorbent was spontaneous. This work has demonstrated that chitosan-iron nanowires in porous anodic alumina as an adsorbent has promising potential for heavy metal removal at trace level.     

Biosorption of Cr(VI) from Water Using Biomass of <Emphasis Type="Italic">Aeromonas hydrophila</Emphasis>: Central Composite Design for Optimization of Process Variables

The potential use of biomass of Aeromonas hydrophila for biosorption of chromium from aqueous solution was investigated. The variables (pH, initial Cr(VI) concentration, biomass dose, and temperature) affecting process were optimized by performing minimum number of experimental runs with the help of central composite design. The results predicted by design were found to be in good agreement (R ² = 99.1%) with those obtained by performing experiments. Multiple regression analysis shows that uptake decreases with increase in pH and biomass dose, whereas it increases with increase in temperature and concentration. The maximum removal of Cr(VI) predicted by contour and optimization plots was 184.943 mg/g at pH 1.5, initial Cr(VI) concentration 311.97 mg/L, temperature 60 °C, and biomass dose 1.0 g. The removal of Cr(VI) was governed by adsorption of Cr(VI) as well as its reduction into Cr(III), which further gets adsorbed. The sorption capacity of biomass was calculated from experimental data using Langmuir sorption model and was found to be 151.50 mg/g at 40 °C and pH 1.5, which is comparable to other biosorbents. In addition to this, Dubinin–Radushkevich model was applied, and it was found that nature of sorption was chemisorption.     

Evaluation of vermicompost as bioadsorbent substrate of Pb,Ni, V and Cr for waste waters remediation using Total Reflection X-ray Fluorescence

The use of vermicompost as adsorbent substrate for removing Pb, Ni, V and Cr from waste waters is proposed. In this work, after a preliminary physical and chemical characterization of the vermicompost, the optimal parameters for the heavy metal adsorption were obtained. A synthetic multielemental solution of Pb, Cr and Ni and a solution of NH₄VO₃ for vanadium were evaluated. The optimized parameters were pH, vermicompost mass to volume ratio, agitation time and particle size of the adsorbent. A batch system was employed for the assays. The elements were determined in the supernatant solution after filtration of the substrate. An optimal pH of 4.5 was found for ion removal. The agitation time slightly influences the adsorption of Pb and Cr, but it has a high influence on the Ni and V adsorption. The highest adsorption and removal of the metals was observed for a vermicompost mass of 2 g per 500 mL using a particle size between 75 to 841 µm for Pb, Cr and Ni, and 841 till 1192 µm for V. The mean removal percentage for each element is around 95% for Pb. Ni and Cr in the multielemental synthetic sample, demonstrating a high removal capacity of the substrate. For V it was found a removal efficiency of 50%.     

Removal of uranium(VI) from aqueous solution by apricot shell activated carbon

Uranium is a toxic and radioactive heavy metal found in nuclear effluents and should be treated based on environmental considerations. The adsorption of uranyl cations (UO₂ ²⁺) by apricot shell activated carbon (ASAC) was investigated in a batch system. The effects of pH, contact time, temperature, adsorbent dosage on the adsorption kinetics and equilibrium adsorption isotherms of U(VI) were examined. The U(VI) uptake was fast within the first 60 min and reached an equilibrium state at 120 min. The adsorption process was highly pH dependent and the maximum adsorption was obtained at an initial solution pH of 6.0. Temperature over the range 25–45 °C had little effect on the U(VI) adsorption. The U(VI) removal efficiency increased concurrently with increasing ASAC dosage, whereas the U(VI) adsorption capacity decreased with increasing ASAC dosage. The adsorption process followed both Langmuir and Freundlich isotherms. On the basis of Langmuir model, the maximum adsorption capacity was found to be 59.17 mg U(VI)/g adsorbent. The adsorption kinetics can be very well defined by the pseudo-first-order rate model. The present results suggest that ASAC could be used as an adsorbent for an efficient removal of U(VI) from aqueous solution.     

Adsorption of Chromium (VI) on <Emphasis Type="Italic">Azadirachta Indica</Emphasis> (Neem) Leaf Powder

A novel adsorbent was developed from mature leaves of the Neem tree (Azadirachta Indica) for removing metal ions from water. The adsorbent, in the form of fine powder, was found to be very effective in removing chromium (VI) from aqueous solution. The adsorption was carried out in a batch process taking different concentrations of the metal ion in aqueous solution with variation in adsorbent amount, pH, agitation time and temperature. The suitability of the adsorbent was tested with Langmuir and Freundlich isotherms and with various equilibrium kinetic data. A small amount of the Neem Leaf Powder (NLP) (1.6 g dm^–3) could remove as much as 87% of Cr (VI) in 300 min from a solution of concentration 14.1 mg dm^–3 at 300 K. The optimum range of pH for the adsorption process was 4.5–7.5 and since the natural pH of the Cr (VI) solution was 5.5, no addition of acid or alkali was necessary for achieving maximum adsorption. The adsorption coefficients indicated a high potentiality for the NLP to be used as an adsorbent for removing Cr (VI) from water.     

Removal, preconcentration and determination of Mo(VI) from water and wastewater samples using maghemite nanoparticles

Removal and recovery of Mo(VI) from aqueous solutions were investigated using maghemite (γ-Fe₂O₃) nanoparticles. Combination of nanoparticle adsorption and magnetic separation was used to the removal and recovery of Mo(VI) from water and wastewater solutions. The nanoscale maghemite with mean diameter of 50 nm was synthesized by reduction coprecipitation method followed by aeration oxidation. Various factors influencing the adsorption of Mo(VI), e.g. pH, temperature, initial concentration, and coexisting common ions were studied. Adsorption reached equilibrium within <10 min and was independent of initial concentration of Mo(VI). Studies were performed at different pH values to find out the pH at which maximum adsorption occurred. The maximum adsorption occurred at pHs between 4.0 and 6.0. The Langmuir adsorption capacity (q_max) was found to be 33.4 mg Mo(VI)/g of the adsorbent. The results showed that nanoparticle (γ-Fe₂O₃) is suitable for the removal of Mo(VI), as molybdate, from water and wastewater samples. The adsorbed Mo(VI) was then desorbed and determined spectrophotometrically using bromopyrogallol red as a complexation reagent. This allows the determination of Mo(VI) in the range 1.0–86.0 ng mL⁻¹.     

Adsorption of U(VI) from aqueous solution by cross-linked rice straw

Adsorption of U(VI) from aqueous solution by cross-linked rice straw(CRS) was studied with batch experiments. The adsorbent was characterized by Fourier transform infrared spectroscopy (FT-IR). The effect of contact time, initial pH, temperature, adsorbent amount and initial U(VI) concentration was investigated. Langmuir, Freundlich and Dubinin–Radushkevich (D–R) adsorption isotherms and two kinetic models of pseudo-first-order and pseudo-second-order were used to describe the adsorption process. The result showed that the adsorption process was highly pH dependent and the favorable initial pH was 5.0. The adsorption process was rapid within first 60 min and equilibrium reached at 100 min. The adsorption process could be well defined by the Langmuir isotherm and pseudo-second-order equation, which indicated that the chemical adsorption was the rate-limiting step. The thermodynamic parameters (?H°, ?S°, ?G°) of the adsorption system were also calculated. The negative value of ?H° and ?G° indicated that the reaction was endothermic and spontaneous in nature. All the above suggested that CRS has considerable potential for the removal of U(VI) from aqueous solution.     

Polyvinyl alcohol fibers with functional phosphonic acid group: synthesis and adsorption of uranyl (VI) ions in aqueous solutions

PVA functionalized with vinylphosphonic acid was prepared as a new adsorbent for uranyl (VI) adsorption from aqueous solutions. The vinylphosphonic acid was cografted onto PVA fibers by preirradiation grafting technique. The adsorbent were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The adsorbent was observed to possess a fibrous structure and was bonded with phosphonic acid groups successfully. The adsorbent was used for the adsorption of low levels uranyl (VI) ions from aqueous solutions. The influence of analytical parameters including pH, adsorption time, amount of adsorbent, metal ion concentration, and temperature were investigated on the recovery of uranyl (VI) ion in aqueous solution. The maximum adsorption capacity (32.1 mg g^?1) and fast equilibrium time (30 min) were achieved at pH of 4.5 at room temperature. Thermodynamic parameters (ΔH° = 2.695 kJ mol^?1; ΔS° = 31.15 J mol^?1 K^?1; ΔG° = ?6.748 kJ mol^?1) show the adsorption of an exothermic process and spontaneous nature, respectively. The possible coordination mechanism was illustrated. Adsorption and desorption coexist in aqueous solutions and then the system becomes equilibrium.     

Laterite clay-based geopolymer as a potential adsorbent for the heavy metals removal from aqueous solutions

This study is focused on the investigation of low iron lateritic clay-based geopolymer as a potential adsorbent for the higher uptake of Ni(II) and Co(II) ions from aqueous solutions. BET analysis revealed that the sieved geopolymer sample (SGS) was characterized by 17.441 m²/g of surface area, 0.005 cm³/g of pore volume, and 13.549 Å of pore diameter. SEM investigation confirmed the presence of pores and cavities onto the surface of SGS. XRD analysis showed that the geopolymer is semi-crystalline in nature. It was found that the adsorption ability of SGS remained 520 mg/g for Ni(II) ions and 500 mg/g for Co(II) ions when 0.5 M solutions were stirred with SGS for 60 min. The temperature and pH of the solution were maintained at 60 °C and 7.0, respectively. The adsorption data of both heavy metal (HM) ions fitted best in the pseudo-second-order kinetic model. The low activation energy value i.e. 2.507 kJ/mol for Ni(II) ions and 2.286 kJ/mol for Co(II) ions confirmed adsorption is physisorption. Adsorption data were tested with Langmuir and Freundlich models, the data showed comparatively better fitting in the Freundlich model. The greater value of monolayer adsorption capacity (Xm) for Ni(II) ions was found 1.77 × 10⁻² mol/g while for Co(II) ions it remained 1.69 × 10⁻² mol/g confirming the better interaction of metal ions with the adsorbent surface. Negative values of ΔG° confirmed the spontaneity of the process while the positive value of ΔS° showed the randomness of adsorbate particles. The positive value of ΔH° showed that the adsorption process remained endothermic for both HM ions. The experimental results confirmed the ability of laterite clay-based geopolymer for better removal of HM ions and hence can be employed for the wastewater treatment processes at low-cost adsorbent.     

Evaluation of Acacia nilotica as a non conventional low cost biosorbent for the elimination of Pb(II) and Cd(II) ions from aqueous solutions

In the present study a biomass derived from the leaves of Acacia nilotica was used as an adsorbent material for the removal of cadmium and lead from aqueous solution. The effect of various operating variables, viz., adsorbent dosage, contact time, pH and temperature on the removal of cadmium and lead has been studied. Maximum adsorption of cadmium and lead arises at a concentration of 2 g/50 ml and 3 g/50 ml and at a pH value of 5 and 4, respectively. The sorption data favored the pseudo-second-order kinetic model. Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were applied to describe the biosorption isotherm of the metal ions by A. nilotica biomass. Based on regression coefficient, the equilibrium data found were fitted well to the Langmuir equilibrium model than other models. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) have been calculated, respectively revealed the spontaneous, endothermic and feasible nature of adsorption process. The activation energy of the biosorption (Ea) was estimated as 9.34 kJ mol⁻¹ for Pb and 3.47 kJ mol⁻¹ for Cd from Arrhenius plot at different temperatures.     

Adsorption of Cr (VI) by treated weed <Emphasis Type="Italic">Salvinia cucullata</Emphasis>: kinetics and mechanism

In the present study a new low cost, easily available and environmentally friendly adsorbent was used for removal of Cr (VI). The Cr (VI) removal efficiency of the adsorbent was studied as a function of contact time, pH, adsorbent dose, adsorbate concentration, temperature and stirring speed. Different adsorption model equations for kinetics, isotherm and rate mechanism of the process were used to find the best model, which fit well to the experimental data. A full factorial design of n^k type was used to find a mathematical relation between the percentage of adsorption and variables affecting the adsorption process such as time, pH, adsorbate concentration and temperature. Using the Students ‘t’ test, the significance of each term of the derived equation was tested. The insignificant terms were removed from the derived equation. The adequacy of the equation after removing the insignificant terms was tested using the Fisher adequacy test. From the factorial design analysis it is found that pH has the most pronounced effect followed by time, temperature and the adsorbate concentration. A column study was performed using the optimum operating conditions.     

Sorptive and thermal properties of red clay in relation to Cr(VI)

The results of Cr(VI) adsorption on the red clay modified by hexadecyltrimethylammonium bromide are given. The adsorption isotherm of Cr(VI) is determined based on the Langmuir–Freundlich model and exhibits the adsorption capacity of 0.0005 mol/g in relation to Cr(VI). The study of the pH effect showed that the optimal pH range corresponding to the Cr(VI) adsorption maximum on this clay is 2–6.5. Thermal analysis of the modified adsorbent, i.e., Na/HDTMA-clay, shows two DTG peaks at 58–61 and 241 °C. The first one is a consequence of dehydration of the modified clay sample. The other DTG peak results from evaporation and pyrolysis of HDTMA adsorbed on the clay. In the case of Na/HDTMA-Cr-clay three peaks appear at: 64, 232, and 340 °C. The third DTG peak is related to the oxidation of surfactant. Moreover, the raw mineral shows the peak at 543 °C attributed to the clay dehydroxylation.